Sample records for boron-doped diamond electrodes

Highlights: → Steam activation of borondopeddiamond (BDD) electrodes. → Steam activated BDD has a porous columnar texture. → Steam activated BDD has a wide potential window. - Abstract: Borondopeddiamond (BDD) electrodes were activated in steam at various temperatures, resulting in high quality BDD electrodes with a porous microstructure. Distinct columnar structures were observed by scanning electron microscopy. The electrochemically active surface area of the steam-activated BDD was up to 20 times larger than the pristine BDD electrode owing to the porous texture. In addition, a widening of the potential window was observed after steam activation, suggesting that the quality of BDD was enhanced due to oxidative removal of graphitic impurities during the activation process.

A novel diamond anvil cell suitable for electrical transport measurements under high pressure has been developed. A boron-doped metallic diamond film was deposited as an electrode on a nano-polycrystalline diamond anvil using a microwave plasma-assisted chemical vapor deposition technique combined with electron beam lithography. The maximum pressure that can be achieved by this assembly is above 30 GPa. We report electrical transport measurements of Pb up to 8 GPa. The boron-doped metallic diamondelectrodes showed no signs of degradation after repeated compression.

Full Text Available The electrochemical processes occurring at both edges of the wide electrochemical window of the borondopeddiamond (BDD electrode were studied by polarization curves experiments to evaluate the apparent energy of activation for the rate determining step in each reaction. It was found that the hydrogen evolution reaction occurs by a Volmer-Heyrovsky mechanism with the first step being the RDS. Moreover, the apparent energy of activation calculated from the Tafel plots presented a value as high as 150 kJ mol-1, indicating the formation of the M-H intermediate that is characteristic for the Volmer step. On the other hand, the apparent energy of activation for the oxygen evolution reaction was found to be 106 kJ mol-1 suggesting that the RDS in this mechanism is the initial adsorption step. In this way, it was demonstrated that the interaction between water molecules and the electrode surface is strongly inhibited on BDD thus justifying the extended potential window observed for this material.

We present a microfluidic electrochemical cell with integrated borondopeddiamond (BDD) electrodes which is designed for high electrochemical conversion efficiencies. With our newest developments, we aim to exploit the benefits of BDD as a novel electrode material to conduct tyrosine- and

Electrochemical oxidation of peptides and proteins is traditionally performed on carbon-based electrodes. Adsorption caused by the affinity of hydrophobic and aromatic amino acids toward these surfaces leads to electrode fouling. We compared the performance of boron-dopeddiamond (BDD) and glassy

Full Text Available Electrochemical studies of diamond were started more than fifteen years ago with the first paper on diamond electrochemistry published by Pleskov. After that, work started in Japan, United States of America, France, Switzerland and other countries. Over the last few years, the number of publications has increased considerably. Diamond films have been the subject of applications and fundamental research in electrochemistry, opening up a new branch known as the electrochemistry of diamondelectrodes. Here, we first present a brief history and the process of diamond film synthesis. The principal objective of this work is to summarize the most important results in the electrochemical oxidation using diamondelectrodes.

Electrochemical studies of diamond were started more than fifteen years ago with the first paper on diamond electrochemistry published by Pleskov. After that, work started in Japan, United States of America, France, Switzerland and other countries. Over the last few years, the number of publications has increased considerably. Diamond films have been the subject of applications and fundamental research in electrochemistry, opening up a new branch known as the electrochemistry of diamondelectrodes. Here, we first present a brief history and the process of diamond film synthesis. The principal objective of this work is to summarize the most important results in the electrochemical oxidation using diamondelectrodes. (author)

Boron-dopeddiamond (BDD) thin films, as one kind of electrode materials, are superior to conventional carbon-based materials including carbon paste, porous carbon, glassy carbon (GC), carbon nanotubes in terms of high stability, wide potential window, low background current, and good biocompatibility. Electrochemical biosensor based on BDD electrodes have attracted extensive interests due to the superior properties of BDD electrodes and the merits of biosensors, such as specificity, sensitiv...

Synthetic boron-dopeddiamond (BDD) thin film is an electrode material with high chemical and dimensional stability, low background current and a very wide potential window of water stability. Upon anodic polarization, BDD generates hydroxyl radicals that mediate the oxidation processes in the vicinity of the electrode surface. These hydroxyl radials are assumed to be free, i.e., not adsorbed on the electrode surface. Hydroxyl radicals are formed on BDD during water discharge, which is the ra...

Graphical abstract: Display Omitted -- Abstract: This paper presents for the first time the study of electrochemical behavior of well known immunosuppressant drug – rapamycin (sirolimus) using boron-dopeddiamondelectrode. Rapamycin provided single and oval-shaped oxidation peak at +1.1 V vs. Ag/AgCl electrode in Britton–Robinson buffer solution at pH 3 confirming highly irreversible behavior of analyte at boron-dopeddiamondelectrode. A differential pulse voltammetry was used for quantification of tested drug under the optimum experimental conditions. The calibration curve was linear over the range from 0.5 to 19.5 μM (R 2 = 0.9976) with detection limit of 0.22 μM. Repeatability of ten successfully measurements of three different concentrations (5, 10 and 15 μM) was 2.5, 1.9 and 1,7 %, respectively. Influence of most common biomolecules presented in urine samples was evaluated. The suggested analytical methodology was successfully applied for determination of rapamycin in four urine samples with excellent recoveries. The developed approach could be beneficial in analysis of rapamycin in biological samples using boron-dopeddiamondelectrode as up-to-date electrochemical sensor and could represent inexpensive analytical alternative to separation methods

Boron-dopeddiamond (BDD) electrodes are recognized as being superior to other electrode materials due to their outstanding chemical and dimensional stability, their exceptionally low background current, the extremely wide potential window for water electrolysis that they have, and their excellent biocompatibility. However, whereas these properties have been utilized in the rapid development of electroanalytical applications, very few studies have been done in relation to their applications in electrocatalysis or electrosynthesis. In this report, following on from reports of the electrosynthesis of various products through anodic and cathodic reactions using BDD electrodes, the potential use of these electrodes in electrosynthesis is discussed.

In recent years, conductive diamondelectrodes for electrochemical applications have been a major focus of research and development. The impetus behind such endeavors could be attributed to their wide potential window, low background current, chemical inertness, and mechanical durability. Several analytes can be oxidized by conducting diamond compared to other carbon-based materials before the breakdown of water in aqueous electrolytes. This is important for detecting and/or identifying species in solution since oxygen and hydrogen evolution do not interfere with the analysis. Thus, conductive diamondelectrodes take electrochemical detection into new areas and extend their usefulness to analytes which are not feasible with conventional electrode materials. Different types of diamondelectrodes, polycrystalline, microcrystalline, nanocrystalline and ultrananocrystalline, have been synthesized and characterized. Of particular interest is the synthesis of boron-dopeddiamond (BDD) films by chemical vapor deposition on various substrates. In the tetrahedral diamond lattice, each carbon atom is covalently bonded to its neighbors forming an extremely robust crystalline structure. Some carbon atoms in the lattice are substituted with boron to provide electrical conductivity. Modification strategies of doped diamondelectrodes with metallic nanoparticles and/or electropolymerized films are of importance to impart novel characteristics or to improve the performance of diamondelectrodes. Biofunctionalization of diamond films is also feasible to foster several useful bioanalytical applications. A plethora of opportunities for nanoscale analytical devices based on conducting diamond is anticipated in the very near future.

Full Text Available Boron-dopeddiamond (BDD thin films, as one kind of electrode materials, are superior to conventional carbon-based materials including carbon paste, porous carbon, glassy carbon (GC, carbon nanotubes in terms of high stability, wide potential window, low background current, and good biocompatibility. Electrochemical biosensor based on BDD electrodes have attracted extensive interests due to the superior properties of BDD electrodes and the merits of biosensors, such as specificity, sensitivity, and fast response. Electrochemical reactions perform at the interface between electrolyte solutions and the electrodes surfaces, so the surface structures and properties of the BDD electrodes are important for electrochemical detection. In this paper, the recent advances of BDD electrodes with different surfaces including nanostructured surface and chemically modified surface, for the construction of various electrochemical biosensors, were described.

Boron-dopeddiamond (BDD) is a prospective electrode material that possesses many exceptional properties including wide potential window, low noise, low and stable background current, chemical and mechanical stability, good biocompatibility, and last but not least exceptional resistance to passivation. These characteristics extend its usability in various areas of electrochemistry as evidenced by increasing number of published articles over the past two decades. The idea of chemically modifying BDD electrodes with molecular species attached to the surface for the purpose of creating a rational design has found promising applications in the past few years. BDD electrodes have appeared to be excellent substrate materials for various chemical modifications and subsequent application to biosensors and biosensing. Hence, this article presents modification strategies that have extended applications of BDD electrodes in electroanalytical chemistry. Different methods and steps of surface modification of this electrode material for biosensing and construction of biosensors are discussed.

Full Text Available Electrochemical incineration using boron-dopeddiamondelectrodes was applied to samples obtained from a refinery and compared to the photo-electro-Fenton process in order to selectively eliminate the phenol and phenolic compounds from a complex matrix. Due to the complex chemical composition of the sample, a pretreatment to the sample in order to isolate the phenolic compounds was applied. The effects of the pretreatment and of pH on the degradation of the phenolic compounds were evaluated. The results indicate that the use of a boron-dopeddiamondelectrode in an electrochemical incineration process mineralizes 99.5% of the phenolic sample content. Working in acidic medium (pH = 1, and applying 2 A at 298 K under constant stirring for 2 hours, also results in the incineration of the reaction intermediates reflected by 97% removal of TOC. In contrast, the photo-electro-Fenton process results in 99.9% oxidation of phenolic compounds with only a 25.69% removal of TOC.

The aim of this study was to investigate the feasibility of depositing a thin layer of boron-doped nanocrystalline diamond (B-NCD) on titanium nitride (TiN) coated electrodes and the effect this has on charge injection properties. The charge storage capacity increased by applying the B-NCD film...

Boron-dopeddiamond (BDD) and SnO 2 electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) and sol–gel method, respectively. Electrochemical characterization of the two electrodes were investigated by phenol electrochemical degradation, accelerated service life test, cyclic voltammetry (CV) in phenol solution, polarization curves in H 2 SO 4 . The surface morphology and crystal structure of two electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. The results showed a considerable difference between the two electrodes in their electrocatalytic activity, electrochemical stability and surface properties. Phenol was readily mineralized to CO 2 at BDD electrode, favoring electrochemical combustion, but its degradation was much slower at SnO 2 electrode. The service life of BDD electrode was 10 times longer than that of SnO 2 . Higher electrocatalytic activity and electrochemical stability of BDD electrode arise from its high oxygen evolution potential and the physically absorbed hydroxyl radicals (·OH) on electrode surface.

The paper reports on the formation of carboxy-terminated boron-dopeddiamond (BDD) electrodes. The carboxylic acid termination was prepared in a controlled way by reacting photochemically oxidized BDD with succinic anhydride. The resulting interface was readily employed for the linking of an amine-terminated ligand such as an osmium complex bearing an amine terminal group. The interfaces were characterized using X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV). Contact angle measurements were used to follow the changes in surface wetting properties due to surface functionalization. The chemical reactivity of the carboxyl-terminated BDD was investigated by covalent coupling of the acid groups to an amine-terminated osmium complex.

A prototype microfluidic device using boron-dopeddiamond (BDD) electrodes patterned on an alumina chip was designed and fabricated. Electrochemical microfluidic devices have advantages in that the amount of sample required is small, the measurement throughput is high, different functions can be integrated on a single device, and they are highly durable. In using the device for the flow injection analysis of oxalic acid, the application of a brief conditioning step ensured that the reproducibility of the current signal was excellent. Furthermore, the fabricated system also performed as a prototype of “elimination-detection flow system”, in which interfering species are eliminated using “elimination electrodes” prior to the species reaching the “detection electrode”. The fabricated device reduced the current due to interfering species by 78%. Designs of devices to improve this efficiency are also discussed.

Boron-dopeddiamond (BDD) is a promising electrode material for use in the spectro-electrochemical study of redox proteins and, in this investigation, cyclic voltammetry was used to obtain quasi-reversible electrochemical responses from two blue copper proteins, parsley plastocyanin and azurin from Pseudomonas aeruginosa. No voltammetry was observed at the virgin electrodes, but signals were observed if the electrodes were anodised, or abraded with alumina, prior to use. Plastocyanin, which has a considerable overall negative charge and a surface acidic patch which is important in forming a productive electron transfer complex with its redox partners, gave a faradaic signal at pre-treated BDD only in the presence of neomycin, a positively charged polyamine. The voltammetry of azurin, which has a small overall charge and no surface acidic patch, was obtained identically in the presence and absence of neomycin. Investigations were also carried out into the voltammetry of two site-directed mutants of azurin, M64E azurin and M44K azurin, each of which introduce a charge into the protein's surface hydrophobic patch. The oxidizing and cleaning effects of the BDD electrode pre-treatments were studied electrochemically using two inorganic probe ions, Fe(China){sub 6} {sup 3-} and Ru(NH{sub 3}){sub 6} {sup 3+}, and by X-ray photoelectron spectroscopy (XPS). All of the electrochemical results are discussed in relation to the electrostatic and hydrophobic contributions to the protein/diamond electrochemical interaction.

Highlights: • Nanodiamonds (NDs) were electrophoretically deposited on the BDD film. • The NDs significantly extended the potential window. • Ni/NDs/BDD electrode was prepared by electrodeposition. • The electrode shows good catalytic activity for glucose oxidation. - Abstract: A stable and sensitive non-enzymatic glucose sensor was prepared by modifying a boron-dopeddiamond (BDD) electrode with nickel (Ni) nanosheets and nanodiamonds (NDs). The NDs were electrophoretically deposited on the BDD surface, and acted as nucleation sites for the subsequent electrodeposition of Ni. The morphology and composition of the modified BDD electrodes were characterized by field-emission scanning electron microscopy and energy-dispersive X-ray spectroscopy, respectively. The Ni nanosheet-ND modified BDD electrode exhibited good current response towards the non-enzymatic oxidation of glucose in alkaline media. The NDs significantly extended the potential window. The response to glucose was linear over the 0.2–1055.4-μM range. The limit of detection was 0.05 μM, at a signal-to-noise ratio of 3. The Ni nanosheet-ND/BDD electrode exhibited good selectivity, reproducibility and stability. Its electrochemical performance, low cost and simple preparation make it a promising non-enzymatic glucose sensor.

Carbon based electrodes are widely used for in vivo and in vitro electrochemical studies. In particular, monoamine neurochemistry has been investigated using carbon microfibre electrodes. Similarly, glassy carbon (GC) is the preferred material for many biochemical applications, such as electrochemical detection in chromatography. More recently, borondopeddiamond (BDD) has been utilized for biosensing, as its carbon sp 3 structure is expected to provide better resistance to analyte fouling. However, the main factor limiting the use of electrochemical sensors for biological studies is the effect of the biological matrix. Indeed, in vivo or in situ measurements expose the sensor to a complex matrix of proteins, which adsorb on the sensing surface and interfere with the electrochemical measurements. Here, we compare the performance of three carbon based electrodes: GC, GC with low surface oxides and BDD. The redox species ruthenium(III) hexaammine (outer-sphere), ferrocyanide (surface sensitive) and the biologically significant dopamine have been investigated in protein and blood-mimicking matrices. Cyclic voltammetry and electrochemical impedance spectroscopy have been used to examine the effect of spectator molecules and reaction products on electrode mechanisms. Our results show that BDD generally exhibits the best performance for most conditions and reactions and should therefore be preferred for measurements in biologically fouling environments. Furthermore, surface oxides seem also to improve resistance of the GC electrode to biofouling.

Fosamprenavir is a pro-drug of the antiretroviral protease inhibitor amprenavir and is oxidizable at solid electrodes. The anodic oxidation behavior of fosamprenavir was investigated using cyclic and linear sweep voltammetry at boron-dopeddiamond and glassy carbon electrodes. In cyclic voltammetry, depending on pH values, fosamprenavir showed one sharp irreversible oxidation peak or wave depending on the working electrode. The mechanism of the oxidation process was discussed. The voltammetric study of some model compounds allowed elucidation of the possible oxidation mechanism of fosamprenavir. The aim of this study was to determine fosamprenavir levels in pharmaceutical formulations and biological samples by means of electrochemical methods. Using the sharp oxidation response, two voltammetric methods were described for the determination of fosamprenavir by differential pulse and square-wave voltammetry at the boron-dopeddiamond and glassy carbon electrodes. These two voltammetric techniques are 0.1 M H(2)SO(4) and phosphate buffer at pH 2.0 which allow quantitation over a 4 x 10(-6) to 8 x 10(-5) M range using boron-dopeddiamond and a 1 x 10(-5) to 1 x 10(-4) M range using glassy carbon electrodes, respectively, in supporting electrolyte. All necessary validation parameters were investigated and calculated. These methods were successfully applied for the analysis of fosamprenavir pharmaceutical dosage forms, human serum and urine samples. The standard addition method was used in biological media using boron-dopeddiamondelectrode. No electroactive interferences from the tablet excipients or endogenous substances from biological material were found. The results were statistically compared with those obtained through an established HPLC-UV technique; no significant differences were found between the voltammetric and HPLC methods.

Full Text Available Building on diamond characteristics such as hardness, chemical inertness and low electron emission threshold voltage, the current microscopic, spectroscopic and voltammetric investigations are directed towards improving the properties of electrode coating materials for their future use in clinical studies of deep brain stimulation via fast-scan cyclic voltammetry (FSCV. In this study we combine the capabilities of confocal Raman mapping in providing detailed and accurate analysis of local distributions of material constituents in a series of boron-doped polycrystalline diamond films grown by chemical vapor deposition, with information from the more conventional techniques of scanning electron microscopy (SEM and infrared absorption spectroscopy. Although SEM images show a uniform distribution of film crystallites, they have the limitation of being unable to differentiate the distribution of boron in the diamond. Values of 1018–1021 atoms/cm3 of boron content have been estimated from the absorption coefficient of the 1290 cm−1 infrared absorption band and from the 500 cm−1 Raman vibration. The observed accumulation of boron atoms and carbon sp2 impurities at the grain boundaries suggests that very high doping levels do not necessarily contribute to improvement of the material’s conductivity, corroborating with voltammetric data. FSCV results also indicate an enhanced stability of analyte detection.

Full Text Available A gas diffusion sequential injection system with amperometric detection using aboron-doped diamondelectrode was developed for the determination of sulfite. A gasdiffusion unit (GDU was used to prevent interference from sample matrices for theelectrochemical measurement. The sample was mixed with an acid solution to generategaseous sulfur dioxide prior to its passage through the donor channel of the GDU. Thesulfur dioxide diffused through the PTFE hydrophobic membrane into a carrier solution of 0.1 M phosphate buffer (pH 8/0.1% sodium dodecyl sulfate in the acceptor channel of theGDU and turned to sulfite. Then the sulfite was carried to the electrochemical flow cell anddetected directly by amperometry using the boron-dopeddiamondelectrode at 0.95 V(versus Ag/AgCl. Sodium dodecyl sulfate was added to the carrier solution to preventelectrode fouling. This method was applicable in the concentration range of 0.2-20 mgSO32Ã¢ÂˆÂ’/L and a detection limit (S/N = 3 of 0.05 mg SO32Ã¢ÂˆÂ’/L was achieved. This method wassuccessfully applied to the determination of sulfite in wines and the analytical resultsagreed well with those obtained by iodimetric titration. The relative standard deviations forthe analysis of sulfite in wines were in the range of 1.0-4.1 %. The sampling frequency was65 hÃ¢ÂˆÂ’1.

The kinetics and mechanism of the deep oxidation of sodium diclofenac on a boron-dopeddiamondelectrode are studied to develop a technique for purifying wastewater from pharmaceutical products. The products of sodium diclofenac electrolysis are analyzed using cyclic voltammetry and nuclear magnetic resonance techniques. It is shown that the toxicity of the drug and products of its electrolysis decreases upon its deep oxidation.

Aim of this work is to discuss the electrochemical oxidation of oxalic acid (OA), analyzing the influence of NaCl and NaBr. Experiments were carried out at boron-dopeddiamond (BDD) electrodes, in alkaline media. BDD electrodes have a poor superficial adsorptivity so their great stability toward oxidation allows the reaction to take place with reactants and intermediates in a non-adsorbed state. The process is significantly accelerated by the presence of a halogen salt in solution; interestingly, the mediated process does not depend on applied current density. Based on the results, bromide was selected as a suitable mediator during OA oxidation at BDD. Br - primarily acts in the volume of the solution, with the formation of strong oxidants; while Cl - action has shown lower improvements in the OA oxidation rate at BDD respect to the results reported using Pt electrode. Finally, the parameters of removal efficiency and energy consumption for the electrochemical incineration of OA were calculated. (author)

Electrochemical oxidation of peptides and proteins is traditionally performed on carbon-based electrodes. Adsorption caused by the affinity of hydrophobic and aromatic amino acids toward these surfaces leads to electrode fouling. We compared the performance of boron-dopeddiamond (BDD) and glassy carbon (GC) electrodes for the electrochemical oxidation and cleavage of peptides. An optimal working potential of 2000 mV was chosen to ensure oxidation of peptides on BDD by electron transfer processes only. Oxidation by electrogenerated OH radicals took place above 2500 mV on BDD, which is undesirable if cleavage of a peptide is to be achieved. BDD showed improved cleavage yield and reduced adsorption for a set of small peptides, some of which had been previously shown to undergo electrochemical cleavage C-terminal to tyrosine (Tyr) and tryptophan (Trp) on porous carbon electrodes. Repeated oxidation with BDD electrodes resulted in progressively lower conversion yields due to a change in surface termination. Cathodic pretreatment of BDD at a negative potential in an acidic environment successfully regenerated the electrode surface and allowed for repeatable reactions over extended periods of time. BDD electrodes are a promising alternative to GC electrodes in terms of reduced adsorption and fouling and the possibility to regenerate them for consistent high-yield electrochemical cleavage of peptides. The fact that OH-radicals can be produced by anodic oxidation of water at elevated positive potentials is an additional advantage as they allow another set of oxidative reactions in analogy to the Fenton reaction, thus widening the scope of electrochemistry in protein and peptide chemistry and analytics.

Quantification of mercury ions at the ppt level is reported using highly boron-dopeddiamond (BDD) film electrodes by differential pulse voltammetry (DPV). The DPV experiments were performed in nitrate, thiocyanate and chloride media. Investigation in chloride medium is important since practical samples usually contain chloride impurities. The formation of calomel in a chloride medium on the BDD surface is avoided by the co-deposition of purposely-added gold (3 ppm) during DPV detection. Excellent linear calibration plots have been obtained in all media for ppb ranges. Mercury in the 0.005-50 ppb range has been detected using a rotating disk electrode (RDE) technique in real samples (KCl impinger solutions) prepared from flue gas released by a pilot-scale coal-fired combustion facility. A portable instrument has also been used for the detection of mercury efficiently. These studies have demonstrated that BDD mounted in an RDE system together with gold co-deposition is able to detect mercury with sufficient sensitivity for practical analysis of environmental samples.

A gold nanoparticle modified boron-dopeddiamondelectrode was developed as a transducer for biochemical oxygen demand (BOD) measurements. Rhodotorula mucilaginosa UICC Y-181 was immobilized in a sodium alginate matrix, and used as a biosensing agent. Cyclic voltammetry was applied to study the oxygen reduction reaction at the electrode, while amperometry was employed to detect oxygen, which was not consumed by the microorganisms. The optimum waiting time of 25 min was observed using 1-mm thickness of yeast film. A comparison against the system with free yeast cells shows less sensitivity of the current responses with a linear dynamic range (R(2) = 0.99) of from 0.10 mM to 0.90 mM glucose (equivalent to 10 - 90 mg/L BOD) with an estimated limit of detection of 1.90 mg/L BOD. However, a better stability of the current responses could be achieved with an RSD of 3.35%. Moreover, less influence from the presence of copper ions was observed. The results indicate that the yeast-immobilized BOD sensors is more suitable to be applied in a real condition.

Porous boron-dopeddiamond (BDD) was prepared by hydrogen-argon plasma etching using electrodeposited Ni nanoparticles as a catalyst. The etching process and formation mechanism of porous BDD were investigated by changing the etching time from 30 s to 300 s. Pores were produced due to the C atoms around Ni nanoparticles are easy to react with hydrogen plasma and form methane. With the increase of etching time, the pore size increased, the pore density decreased, and the pore depth first increased and then maintained unchanged. The sp2-bonded graphitic carbons existing on the surface of BDD increase with increasing etching time due to the increase of surface area. No preferential etching was observed due to the high energy of argon plasma. The electrochemical behaviors of the pristine and porous BDD electrodes were characterized by cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS). The results showed that the porous BDD electrode exhibited high specific capacitance, which is attributed to its high electrical conductivity and large specific surface area. The highest specific capacitance of porous BDD electrode is 9.55 mF cm-2, which is 22 times higher than that of pristine BDD electrode. The specific capacitance retention of the porous BDD electrode reduced to 98.2% of the initial capacitance after 500 cycles and then increased to 120.0% after 10,000 cycles. For the first 500 cycles, the reduction of capacitance can be attributed to the dissolution of Ni nanoparticles that attached on the porous BDD surface or buried in the shallow layer. The capacitance increase after 10,000 cycles is due to the better contact of the electrolytic solution with the residual Ni with the increase of cycle number.

Full Text Available Cyclic voltammetry (CV and chronoamperometry (CA have been used to sense and determine simultaneously L-ascorbic acid (AA and acetaminophen (AC at a boron-dopeddiamondelectrode (BDDE in a Britton-Robinson buffer solution. The calibration plots of anodic current peak versus concentration obtained from CV and CA data for both investigated compounds in single and di-component solutions over the concentration range 0.01 mM Ã¢Â€Â“ 0.1 mM proved to be linear, with very good correlation parameters. Sensitivity values and RSD of 2-3% were obtained for various situations, involving both individual and simultaneous presence of AA and AC. The chronoamperometric technique associated with standard addition in sequential one step and/or two successive and continuous chronoamperograms at two characteristic potential levels represented a feasible option for the simultaneous determination of AA and AC in real sample systems such as pharmaceutical formulations. The average values indicated by the supplier were confirmed to a very close approximation from chronoamperomgrams by using several additions with the application of suitable current correction factors.

The objective of this study is to investigate the potential application of the anodic oxidation (AO) on two electrolytic cells (monopolar (Cell 1) and bipolar (Cell 2)) containing boron-dopeddiamondelectrodes on the treatment of real textile effluents to study the reuse possibility of treated wastewater in the textile industry process. AO is applied in the flocculation coagulation pretreatment of both upstream (BH) and downstream (BS) effluents. The chemical oxygen demand (COD) results show that the final COD removal obtained for the BH effluent in the case of Cell 1 and Cell 2 is 800 and 150 mg O₂L⁻¹ after 5 and 6 h of electrolysis, respectively. The treatments of the BS effluent allow for obtaining a final COD of 76 mg L⁻¹ for Cell 1 and a total mineralization for Cell 2. The obtained results demonstrate that the apparent mineralization kinetics of both effluents when using Cell 2 are about four times faster than the one obtained by Cell 1 and highlight the important contribution of the bipolar cell. Besides, the energy consumption values show that the treatment of the BH effluent by Cell 1 consumes 865 kWh kg COD⁻¹ against 411 kWh kg COD(-1) by Cell 2. Therefore, the use of Cell 2 decreases the energy cost by 2.1-6.65 times when compared to Cell 1 in the case of the BH and BS effluent treatment, respectively.

The electrooxidative behavior and determination of zolmitriptan at a boron-dopeddiamondelectrode were investigated using cyclic, linear sweep, differential pulse and square wave voltammetric techniques. Zolmitriptan undergoes irreversible oxidation at a peak potential of about +0.9 V (vs Ag/AgCl/3 M KCl). DPV and SWV techniques are proposed for the determination of zolmitriptan in phosphate buffer at pH 3.03, which allows quantitation over the two different ranges (8 x 10(-7) - 8 x 10(-6) M and 1 x 10(-5) - 1 x 10(-4) M) in supporting electrolyte for both methods. A linear response was obtained in phosphate buffer over two different ranges (6 x 10(-7) - 8 x 10(-6) M and 1 x 10(-5) - 1 x 10(-4) M) for spiked serum samples at pH 3.03 for both techniques. The repeatability and reproducibility of the methods for all media were determined. The standard addition method was used in serum. Precision and accuracy were also checked in all media. No electroactive interferences from the excipients and endegenous substances were found in the pharmaceutical dosage form and the biological sample, respectively.

Competitive hydrogen evolution and multiple proton-coupled electron transfer reactions limit photoelectrochemical CO2 reduction in aqueous electrolyte. Here, oxygen-terminated lightly boron-dopeddiamond (BDDL) thin films were synthesized as a semiconductor electron source to accelerate CO2 reduction. However, BDDL alone could not stabilize the intermediates of CO2 reduction, yielding a negligible amount of reduction products. Silver nanoparticles were then deposited on BDDL because of their selective electrochemical CO2 reduction ability. Excellent selectivity (estimated CO:H2 mass ratio of 318:1) and recyclability (stable for five cycles of 3 h each) for photoelectrochemical CO2 reduction were obtained for the optimum silver nanoparticle-modified BDDL electrode at −1.1 V vs. RHE under 222-nm irradiation. The high efficiency and stability of this catalyst are ascribed to the in situ photoactivation of the BDDL surface during the photoelectrochemical reaction. The present work reveals the potential of BDDL as a high-energy electron source for use with co-catalysts in photochemical conversion. PMID:27892544

Competitive hydrogen evolution and multiple proton-coupled electron transfer reactions limit photoelectrochemical CO2 reduction in aqueous electrolyte. Here, oxygen-terminated lightly boron-dopeddiamond (BDDL) thin films were synthesized as a semiconductor electron source to accelerate CO2 reduction. However, BDDL alone could not stabilize the intermediates of CO2 reduction, yielding a negligible amount of reduction products. Silver nanoparticles were then deposited on BDDL because of their selective electrochemical CO2 reduction ability. Excellent selectivity (estimated CO:H2 mass ratio of 318:1) and recyclability (stable for five cycles of 3 h each) for photoelectrochemical CO2 reduction were obtained for the optimum silver nanoparticle-modified BDDL electrode at -1.1 V vs. RHE under 222-nm irradiation. The high efficiency and stability of this catalyst are ascribed to the in situ photoactivation of the BDDL surface during the photoelectrochemical reaction. The present work reveals the potential of BDDL as a high-energy electron source for use with co-catalysts in photochemical conversion.

Gold-modified borondopeddiamond (BDD) electrodes were examined for the amperometric detection of oxygen as well as a detector for measuring biochemical oxygen demand (BOD) using Rhodotorula mucilaginosa UICC Y-181. An optimum potential of -0.5 V (vs Ag/AgCl) was applied, and the optimum waiting time was observed to be 20 min. A linear calibration curve for oxygen reduction was achieved with a sensitivity of 1.4 μA mg(-1) L oxygen. Furthermore, a linear calibration curve in the glucose concentration range of 0.1-0.5 mM (equivalent to 10-50 mg L(-1) BOD) was obtained with an estimated detection limit of 4 mg L(-1) BOD. Excellent reproducibility of the BOD sensor was shown with an RSD of 0.9%. Moreover, the BOD sensor showed good tolerance against the presence of copper ions up to a maximum concentration of 0.80 μM (equivalent to 50 ppb). The sensor was applied to BOD measurements of the water from a lake at the University of Indonesia in Jakarta, Indonesia, with results comparable to those made using a standard method for BOD measurement.

The recovery of potable water from space mission wastewater is critical for the life support and environmental health of crew members in long-term missions. NASA estimates reveal that at manned space missions 0.06 kg/person·day of urine is produced, with urea and various salts as its main components. Current spacecraft water reclamation strategies include the utilization of not only multifiltration systems (MF) and reverse osmosis (RO), but also biological components to deal with crew urine streams. In this research we explore the utilization of urease (EC 3.5.1.5) to convert urea directly to nitrogen by the in-situ utilization of the reaction products, to increase the amount of clean water in future space expeditions. First of all, platinum was electrodeposited on borondopeddiamondelectrodes by cycling the potential between -0.2 V and 1.0 V in metal/0.5 M H2SO4 solution. SEM images of the electrodes showed a distribution of platinum nanoparticles ranging between 50 nm and 300 nm. The biochemical reaction of urease in nature produces ammonia and carbon dioxide from urea. Based on this, Cyclic Voltammetry experiments of an ammonium acetate solution at pH 10 were performed showing an anodic peak at -0.3 V vs. Ag/AgCl due to the ammonia oxidation. Then, a urease solution (Jack Bean) was poured into the electrochemical cell and subsequent additions of urea were performed with the potential held at -0.3 V in order to promote ammonia oxidation. Chronoamperometry data shows that with more than five urea additions the enzyme still responding by producing ammonia, which is being subsequently oxidized at the electrode surface and producing molecular nitrogen. This research has tremendous applications for future long-term space missions since the reaction byproducts could be used for a biomass subsystem (in-situ resource recovery), while generating electricity from the same process.

Microcystins (MCs), produced by blue-green algae, are one of the most common naturally occurring toxins found in natural environment. The presence of MCs in drinking water sources poses a great threat to people's health. In this study, the degradation behavior of microcystin-RR on boron-dopeddiamond (BDD) electrode was investigated under galvanostatic conditions. Such parameters as reaction time, supporting electrolyte and applied current density were varied in order to determine their effects on this oxidation process. The experimental results revealed the suitability of electrochemical processes employing BDD electrode for removing MC-RR from the solution. However, the efficient removal of MC-RR only occurred in the presence of sodium chloride that acted as redox mediators and the reaction was mainly affected by the chloride concentration (c(NaCl)) and applied current density (I(appl)). Full and quick removal of 0.50 microg/ml MC-RR in solution was achieved when the operating conditions of c(NaCl) and I(appl) were 20mM and 46.3 mA/cm(2), or 35 mM and 18.2 mA/cm(2) respectively. The kinetics for MC-RR degradation followed a pesudo-first order reaction in most cases, indicating the process was under mass transfer control. As a result of its excellent performance, the BDD technology could be considered as a promising alternative to promote the degradation of MC-RR than chlorination in drinking water supplies.

The invention relates to a single crystal borondoped CVD diamond that has a toughness of at least about 22 MPa m.sup.1/2. The invention further relates to a method of manufacturing single crystal borondoped CVD diamond. The growth rate of the diamond can be from about 20-100 .mu.m/h.

Cadmium sulphide (CdS) nanoparticles were chemically synthesized using reverse micelles microreactor methods. By using different washing treatments, UV-Vis spectroscopy showed that the absorption peaks appeared at 465 nm, 462 nm, 460 nm, and 459 nm respectively for CdS nanoparticles without and with 1, 2, and 3 times washing treatments using pure water. In comparison with the absorbance peak of bulk CdS at 512 nm, the shifted absorption peaks, indicates that the different sizes of CdS can be prepared. Anodic stripping voltammetry of the CdS nanoparticles was then studied at a boron-dopeddiamondelectrode using 0.1 M KClO{sub 4} and 0.1 M HClO{sub 4} as the electrolytes. A scan rate of 100 mV/s with a deposition potential of -1000 mV (vs. Ag/AgCl) for 60 s at a potential scan from -1600 mV to +800 mV (vs. Ag/AgCl) was applied as the optimum condition of the measurements. Highly-accurate linear calibration curves (R{sup 2} = 0.99) in 0.1 M HClO{sub 4} with the sensitivity of 0.075 mA/mM and the limit of detection of 81 µM in 0.1 M HClO{sub 4} can be achieved, which is promising for an application of CdS nanoparticles as a label for biosensors.

Highlights: • B-doped diamond is nanostructured by corrosion-driven modifications occurring at carbonaceous impurity sites (sp 2 -carbons). • The electrochemical oxidation partly transforms a hydrogen-terminated diamond surface to O-terminated one, but the electrocatalytic activity of plasmatically O-terminated diamond is not achieved. • In contrast to all usual sp 2 carbons, the Raman spectra of B-doped diamondelectrodes do not change upon electrochemical charging/discharging. - Abstract: Comparative studies of boron-dopeddiamondselectrodes (polycrystalline, single-crystalline, H-/O-terminated, and with different sp 3 /sp 2 ratios) indicate morphological modifications of diamond which are initiated by corrosion at nanoscale. In-situ electrochemical AFM imaging evidences that the textural changes start at non-diamond carbonaceous impurity sites treated at high positive potentials (>2.2 V vs. Ag/AgCl). The primary perturbations subsequently develop into sub-micron-sized craters. Raman spectroscopy shows that the primary erosion site is graphite-like (sp 2 -carbon), which is preferentially removed by anodic oxidation. Other non-diamond impurity, viz. tetrahedral amorphous carbon (t-aC), is less sensitive to oxidative decomposition. The diamond-related Raman features, including the B-doping-assigned modes, are intact during reversible electrochemical charging/discharging, which is a salient difference from all usual sp 2 -carbons. The electrochemical oxidation partly transforms a hydrogen-terminated diamond surface to O-terminated one, but the electrocatalytic activity of plasmatically O-terminated diamond is not achieved for a model redox couple, Fe 3+/2+ . Electrochemical impedance spectra were fitted to six different equivalent circuits. The determination of acceptor concentrations is feasible even for highly-doped diamondelectrodes.

Boron-dopeddiamond (BDD) electrodes were used to investigate the possibility of detecting trace levels of lead by linear-sweep anodic stripping voltammetry. The low limit of detection (2 nM) is an advantage compared to other electrode materials, and it was found that at low pH values, copper concentrations that are usually present in drinking water do not affect to a large extent the detection of lead. These findings recommend anodic stripping voltammetry at the BDD electrodes as a suitable mercury-free method for the determination of trace levels of lead in drinking water. The results obtained for the lead detection in tap water real samples are in excellent agreement with those found by inductively coupled plasma-mass spectrometry (ICP-MS), demonstrating the practical analytical utility of the method

The electrochemical oxidation of textile effluents over a boron-dopeddiamond anode was investigated in the present study. Experiments were conducted with a multi-component synthetic solution containing seventeen dyes and other auxiliary inorganics, as well as an actual effluent from a textile dyeing process. The effect of varying operating parameters, such as current density (4–50 mA/cm 2 ), electrolyte concentration (0.1–0.5 M HClO 4 ), initial solution pH (1–12.3) and temperature (22–43 °C), on process efficiency was investigated following changes in total organic carbon (TOC), chemical oxygen demand (COD) and color. Complete decolorization accompanied by significant mineralization (up to 85% depending on the conditions) could be achieved after 180 min of treatment. Performance was improved at higher electrolyte concentrations and lower pH values, while the effect of temperature was marginal. Energy consumption per unit mass of COD removed was favored at lower current densities, since energy was unnecessarily wasted to side reactions at higher densities.

The electrochemical degradation of chloride-mediated and chloride-free dye wastewaters was investigated on a boron-dopeddiamond (BDD) electrode in comparison with that on a dimensionally stable anode (DSA), and the applicability of BDD electrode to the degradation of these two kinds of wastewaters was explored. In chloride-free wastewater, the electrochemical degradation efficiency of dye on BDD electrode was much higher than that on DSA, with a chemical oxygen demand (COD) removal of 100% and 26% for BDD and DSA, respectively. In chloride-mediated dye wastewater, COD removal was faster than that in chloride-free wastewater on both BDD and DSA electrodes with COD removal efficiencies higher than 95%, whereas the rate of COD removal on DSA was faster than that on BDD electrode. The investigation indicates that DSA is more suitable than BDD electrode in degradation of originally chloride contained dye wastewaters for the sake of energy and time saving. However, for chloride-free dye wastewaters, with the aim of environmental protection, BDD electrode is more appropriate to realize complete mineralization. At the same time, the secondary pollution can be avoided

The impact of different doping levels of boron-dopeddiamond on the surface functionalization was investigated by means of electrochemical reduction of aryldiazonium salts. The grafting efficiency of 4-nitrophenyl groups increased with the boron levels (B/C ratio from 0 to 20,000 ppm). Controlled grafting of nitrophenyldiazonium was used to adjust the amount of immobilized single-stranded DNA strands at the surface and further on the hybridization yield in dependence on the borondoping level. The grafted nitro functions were electrochemically reduced to the amine moieties. Subsequent functionalization with a succinic acid introduced carboxyl groups for subsequent binding of an amino-terminated DNA probe. DNA hybridization significantly depends on the probe density which is in turn dependent on the borondoping level. The proposed approach opens new insights for the design and control of doped diamond surface functionalization for the construction of DNA hybridization assays.

Highlights: • BDD electrodes with different thickness have been fabricated. • BDD electrodes are used for simultaneous detection of DA and AA. • Anodic pretreatment enhance the separation of DA and AA oxidation peak potential. • Thicker BDD electrode show better performance for DA detection coexisting with AA. - Abstract: In this paper, borondopeddiamond (BDD) with different thickness were prepared by hot filament chemical vapor deposition. The performance of BDD electrodes for detecting dopamine (DA) and ascorbic acid (AA) were investigated. Scanning electron microscopy and Raman spectra reveal the grain size increases and the film quality improves with the increase of film thickness. Electrochemical test show that the transfer coefficient in [Fe{sub 3} (CN) {sub 6}]{sup 3−/4−} redox system increases with the increase of the film thickness. The results of selectivity and sensitivity for DA mixed with AA detection show that 8h-BDD and 12h-BDD electrodes possess well selective separated oxidation peaks of DA and AA, and the 12h-BDD electrode exhibits optimal sensitivity until the DA concentration drops to 1 μ M.

Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent (i.e., hydroxyl radicals) for these measurements; however, these approaches range significantly in their complexity and expense of operation. This research expands upon earlier work to enhance the controllability of boron-dopeddiamond (BDD) electrochemistry as an easily accessible tool for producing hydroxyl radicals in order to oxidize a range of intact proteins. Efforts to modulate the oxidation level while minimizing the adsorption of protein to the electrode involved the use of relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber. Additionally, a different cell activation approach using variable voltage to supply a controlled current allowed us to precisely tune the extent of oxidation in a protein-dependent manner. In order to gain perspective on the level of protein adsorption onto the electrode surface, studies were conducted to monitor protein concentration during electrolysis and gauge changes in the electrode surface between cell activation events. This report demonstrates the successful use of BDD electrochemistry for greater precision in generating a target number of oxidation events upon intact proteins.

The breakdown of pesticides has been promoted by many methods for clean up of contaminated soil and wastewaters. The main goal is to decrease the toxicity of the parent compound to achieve non-toxic compounds or even, when complete mineralization occurs, carbon dioxide and water. Therefore, electrochemical degradation (potentiostatic and galvanostatic) of both the pesticide atrazine and cyanuric acid (CA) at boron-dopeddiamond (BDD) and Ti/Ru0.3Ti0.7O2 dimensionally stable anode (DSA) electrodes, in different supporting electrolytes (NaCl and Na2SO4), is presented with the aim of establishing the influence of the operational parameters on the process efficiency. The results demonstrate that both the electrode material and the supporting electrolyte have a strong influence on the rate of atrazine removal. In the chloride medium, the rate of atrazine removal is always greater than in sulfate under all conditions employed. Furthermore, in the sulfate medium, atrazine degradation was significant only at the BDD electrode. The total organic carbon (TOC) load decreased by 79% and 56% at the BDD and DSA electrodes, respectively, in the chloride medium. This trend was maintained in the sulfate medium but the TOC removal was lower (i.e. 33% and 13% at BDD and DSA electrodes, respectively). CA, a stable atrazine degradation intermediate, was also studied and it is efficiently removed using the BDD electrode in both media, mainly when high current densities are employed. The use of the BDD electrode in the chloride medium not only degrades atrazine but also mineralized cyanuric acid leading to the higher TOC removal.

Highlights: → Electrochemical advanced oxidation process was studied using BDD based anodes with different boron concentrations. → The difference between the non-active and active anodes for organics degradation. → The influence of morphologic and structural properties of BDD electrodes on the RO-16 dye degradation. - Abstract: Boron-dopeddiamond (BDD) films grown on the titanium substrate were used to study the electrochemical degradation of Reactive Orange (RO) 16 Dye. The films were produced by hot filament chemical vapor deposition (HFCVD) technique using two different boron concentrations. The growth parameters were controlled to obtain heavily doped diamond films. They were named as E1 and E2 electrodes, with acceptor concentrations of 4.0 and 8.0 x 10 21 atoms cm -3 , respectively. The boron levels were evaluated from Mott-Schottky plots also corroborated by Raman's spectra, which characterized the film quality as well as its physical property. Scanning Electron Microscopy showed well-defined microcrystalline grain morphologies with crystal orientation mixtures of (1 1 1) and (1 0 0). The electrode efficiencies were studied from the advanced oxidation process (AOP) to degrade electrochemically the Reactive Orange 16 azo-dye (RO16). The results were analyzed by UV/VIS spectroscopy, total organic carbon (TOC) and high-performance liquid chromatography (HPLC) techniques. From UV/VIS spectra the highest doped electrode (E2) showed the best efficiency for both, the aromaticity reduction and the azo group fracture. These tendencies were confirmed by the TOC and chromatographic measurements. Besides, the results showed a direct relationship among the BDD morphology, physical property, and its performance during the degradation process.

The dependency of fossil energy in Indonesia caused the crude oil production to be drastically decreased since 2001, while energy consumption increased. In addition, The use of fossil energy can cause several environmental problems. Therefore, we need an alternative environment-friendly energy as solution for these problems. A microbial fuel cell is one of the prospective alternative source of an environment-friendly energy source to be developed. In this study, Boron-dopeddiamondelectrode was used as working electrode and Candida fukuyamaensis as biocatalyst in microbial fuel cell. Different pH of anode compartment (pH 6.5-7.5) and mediator concentration (10-100 μM) was used to produce an optimal electricity. MFC was operated for 3 hours. During operation, the current and voltage density was measured with potensiostat. The maximum power and current density are 425,82 mW/m2 and 440 mA/m2, respectively, for MFC using pH 7.5 at anode compartment without addition of methylene blue. The addition of redox mediator is lowering the produced electricity because of its anti microbial properties that can kill the microbe.

A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-dopeddiamond (BDD) electrode using square wave voltammetry (SWV) or differential pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 x 10(-7)mol L(-1) to 8.3 x 10(-5)mol L(-1) for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 x 10(-7)mol L(-1) and 3.5 x 10(-8)mol L(-1), respectively. The proposed method was successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level).

This work presents a simple, fast and low-cost methodology for the simultaneous determination of paracetamol (PC) and ibuprofen (IB) in pharmaceutical formulations by differential pulse voltammetry using a boron-dopeddiamond (BDD) electrode. A well-defined oxidation peak was observed using the BDD electrode for each analyte (0.85 V for PC and 1.72 V for IB (vs. Ag/AgCl)) in 0.1 mol L{sup -1} H{sub 2}SO{sub 4} solution containing 10% (v/v) of ethanol. Calibration curves for the simultaneous determination of PC and IB showed a linear response for both drugs in a concentration range of 20 to 400 μmol L{sup -1} (r{sup 2} = 0.999), with a detection limit of 7.1 μmol L{sup -1} for PC and 3.8 μmol L{sup -1} for IB. The addition-recovery studies in samples were about 100% and the results were validated by chromatographic methods. (author)

This work presents a simple, fast and low-cost methodology for the simultaneous determination of paracetamol (PC) and ibuprofen (IB) in pharmaceutical formulations by differential pulse voltammetry using a boron-dopeddiamond (BDD) electrode. A well-defined oxidation peak was observed using the BDD electrode for each analyte (0.85 V for PC and 1.72 V for IB (vs. Ag/AgCl)) in 0.1 mol L -1 H 2 SO 4 solution containing 10% (v/v) of ethanol. Calibration curves for the simultaneous determination of PC and IB showed a linear response for both drugs in a concentration range of 20 to 400 μmol L -1 (r 2 = 0.999), with a detection limit of 7.1 μmol L -1 for PC and 3.8 μmol L -1 for IB. The addition-recovery studies in samples were about 100% and the results were validated by chromatographic methods. (author)

Full Text Available In this paper, the electrochemical behaviour of several parabens preservatives, i.e. esters of p-hydroxybenzoic acid, methyl-, ethyl- and propyl-4-hydroxybenzoates as methyl-, ethyl- and propyl-parabens (MB, EB, and PB, has been investigated at a commercial boron-dopeddiamondelectrode (BDDE, especially in the anodic potential range, in both hydro-alcoholic and aqueous media. The cyclic voltammetric and chronoamperometric measurements yielded calibration plots with very good linearity (R2 between 0.990 and 0.998 and high sensitivity, useful for detection and analytical applications. The determination of the characteristics of individual compounds, of an Ã¢Â€Âœoverall paraben indexÃ¢Â€Â, the assessment of the stability and the saturation solubility in water, and the amperometric sensing and determination in double distilled, tap and river water matrix of the relatively slightly soluble investigated parabens have been carried out using electrochemical alternative. Estimated water solubility was correlated with the octanol-water partition coefficient. Several ideas regarding stability and persistence of the presumptive eco-toxic investigated preservatives in the environment or water systems have been adjacently discussed.

A simple procedure is described for the determination of propylthiouracil (PTU) by differential pulse voltammetry (DPV) using a cathodically pretreated boron-dopeddiamond (BDD) electrode. Cyclic voltammetry studies indicate that the oxidation of PTU is irreversible at a peak potential of 1.42 V (vs. Ag/AgCl (3.0 mol L{sup -1} KCl)) in a Britton-Robinson (BR) buffer solution (pH 2.0). Under optimized conditions, the obtained analytical curve was linear (r = 0.9985) for the PTU concentration range of 1.0 to 29.1 {mu}mol L{sup -1} in a BR buffer solution (pH 2.0), with a detection limit of 0.90 {mu}mol L{sup -1}. The proposed method was successfully applied in the determination of PTU in pharmaceutical samples, with results in agreement at a 95% confidence level with those obtained using an official titration method. (author)

Highlights: ► Unmodified BDD electrode = sensitive electrochemical sensor for drugs determination. ► No special pretreatment of samples except simple dilution. ► Selective method, common compounds present in urine do not interfere in high excess. ► Simultaneous determination of PAR and PEN has yet not been published in literature. - Abstract: A simple, sensitive and selective square-wave voltammetry method for simultaneous determination of paracetamol and penicillin V on a bare (unmodified) boron-dopeddiamondelectrode has been developed. The good potential separation of about 0.35 V between the oxidation peak potentials of both drugs present in mixture was found. It was found by cyclic voltammetry that paracetamol gave quasireversible wave and penicillin V provided irreversible oxidation peak. The effect of supporting electrolyte, pH and scan rate on voltammetric response of both drugs was studied to select the optimum experimental conditions. The optimal conditions for quantitative simultaneous determination were obtained in acetate buffer solution at pH 5.0. The oxidation peak of paracetamol and penicillin V showed a systematic increase in peak currents with increase of their concentration. The calibration curves for the simultaneous determination of paracetamol and penicillin V exhibited the good linear responses within the concentration range from 0.4 to 100 μM for both drugs. The detection limit was established to 0.21 and 0.32 μM for paracetamol and penicillin V, respectively. The method proved the good sensitivity, repeatability (RSD of 1.5 and 2.1% for mixture solution of 10 μM PCM and PEN) and selectivity when influence of interferents commonly existing in human urine was negligible. The practical analytical utility of proposed method was demonstrated by simultaneous determination of paracetamol and penicillin V in human urine samples, with results similar to those obtained using a high-performance liquid chromatography method as an

Diamondelectrode was used to evaluate the interaction of the nucleotides guanosine monophosphate (GMP) and adenosine monophosphate (AMP) with the pesticides chlorpyrifos, methamidophos and monocrotophos. Changes were observed in the currents and peak potentials of the nucleotide voltammograms in the presence of the pesticides, with dependence on the pesticide concentration (from 5.0 × 10 -7 to 5.0 × 10 -5 mol L -1 ) and the interaction time (from 1 min to 4 h). This is probably due to binding of the pesticides to the nitrogenous bases present in the nucleotides, which could lead to problems in the DNA replication and biological functions of nucleotides. The pesticides showed stronger interaction with AMP than with GMP. Studies of the interaction of 50 µg mL -1 DNA with the pesticides (from 30 min to 4 h and from 1.0 × 10 -6 to 6.0 × 10 -5 mol L -1 ) did not reveal any peaks relating to double helix opening or DNA unwinding. (author)

Diamondelectrode was used to evaluate the interaction of the nucleotides guanosine monophosphate (GMP) and adenosine monophosphate (AMP) with the pesticides chlorpyrifos, methamidophos and monocrotophos. Changes were observed in the currents and peak potentials of the nucleotide voltammograms in the presence of the pesticides, with dependence on the pesticide concentration (from 5.0 Multiplication-Sign 10{sup -7} to 5.0 Multiplication-Sign 10{sup -5} mol L{sup -1}) and the interaction time (from 1 min to 4 h). This is probably due to binding of the pesticides to the nitrogenous bases present in the nucleotides, which could lead to problems in the DNA replication and biological functions of nucleotides. The pesticides showed stronger interaction with AMP than with GMP. Studies of the interaction of 50 Micro-Sign g mL{sup -1} DNA with the pesticides (from 30 min to 4 h and from 1.0 Multiplication-Sign 10{sup -6} to 6.0 Multiplication-Sign 10{sup -5} mol L{sup -1}) did not reveal any peaks relating to double helix opening or DNA unwinding. (author)

Full Text Available In this work, voltammetric andelectrolysis experiments have been carried out on a conductive boron dopeddiamond (BDD electrode in solution containing amoxicillin in itspharmaceutical formulation. The physical characterization of the BDD surface byscanning electron microscopy (SEM reveals a polycrystalline structure withgrain sizes ranging between 0.3 and 0.6 µm. With Raman spectroscopy, BDDsurface is composed of diamons (Csp3 type carbon (Csp3and graphitic type carbon (Csp2. The electrochemical characterization of the BDD electrode in sulfuric acid electrolyte showed a wide potential window worthing 2.74 V. The oxidation of Amoxicillin showed an irreversible anodic wave on the voltammogram in the domain of water stability indicating a direct oxidation of amoxicillin at BDD surface. The treatment of Amoxicillin in the synthetic wastewaters under various constant current densities 20, 50, 100, 135 mA cm-2 on BDD showed that Amoxicillin is highly reducedunder 100 mA cm-2 reaching 92% of the Chemical Oxygen Demand (CODremoval after 5 h of electrolysis. Investigation performed in perchloric acidas supporting electrolyte led to 87% of COD removal after 5 h of electrolysis.Mineralization of amoxicillin occurs on BDD and the chemical oxygen demandremoval was higher in sulfuric acid than in perchloric acid owing to theinvolvement of the in-situ formed persulfate and perchlorate to the degradation process mainly in the bulkof the solution. The instantaneous current efficiency (ICE presents anexponential decay indicating that the process was limited by diffusion. Thespecific energy consumed after 5h of the amoxicillin electrolysis was 0.096 kWh COD-1and 0.035 kWh COD-1 in sulfuric acid and in perchloric acidrespectively.

The performance of the electrochemical oxidation process for efficient treatment of domestic wastewater loaded with organic matter was studied. The process was firstly evaluated in terms of its capability of producing an oxidant agent (H2O2) using amorphous carbon (or carbon felt) as cathode, whereas Ti/BDD electrode was used as anode. Relatively high concentrations of H2O2 (0.064 mM) was produced after 90 min of electrolysis time, at 4.0 A of current intensity and using amorphous carbon at the cathode. Factorial design and central composite design methodologies were successively used to define the optimal operating conditions to reach maximum removal of chemical oxygen demand (COD) and color. Current intensity and electrolysis time were found to influence the removal of COD and color. The contribution of current intensity on the removal of COD and color was around 59.1 and 58.8%, respectively, whereas the contribution of treatment time on the removal of COD and color was around 23.2 and 22.9%, respectively. The electrochemical treatment applied under 3.0 A of current intensity, during 120 min of electrolysis time and using Ti/BDD as anode, was found to be the optimal operating condition in terms of cost/effectiveness. Under these optimal conditions, the average removal rates of COD and color were 78.9 ± 2 and 85.5 ± 2 %, whereas 70% of total organic carbon removal was achieved.

Borondopeddiamond (BDD) electrodes have shown considerable promise as an electrode material where many of their reported properties such as extended solvent window, low background currents, corrosion resistance, etc., arise from the catalytically inert nature of the surface. However, if during the growth process, non-diamond-carbon (NDC) becomes incorporated into the electrode matrix, the electrochemical properties will change as the surface becomes more catalytically active. As such it is important that the electrochemist is aware of the quality and resulting key electrochemical properties of the BDD electrode prior to use. This paper describes a series of characterization steps, including Raman microscopy, capacitance, solvent window and redox electrochemistry, to ascertain whether the BDD electrode contains negligible NDC i.e. negligible sp2 carbon. One application is highlighted which takes advantage of the catalytically inert and corrosion resistant nature of an NDC-free surface i.e. stable and quantifiable local proton and hydroxide production due to water electrolysis at a BDD electrode. An approach to measuring the local pH change induced by water electrolysis using iridium oxide coated BDD electrodes is also described in detail. PMID:26779959

Full Text Available The oxidation of iron compounds from alkaline 10 M KOH electrolytes on a borondopeddiamondelectrode is examined by cyclic voltammetry between the potentials of hydrogen evolution reaction and oxygen evolution reaction, due to ferrate(VI electrochemical synthesis. It is shown that the anodic current peak that appears in iron free electrolyte at a less positive potential than the potential of oxygen evolution probably coincides with oxidation of hydrogen in >CH2 groups and C-sp2 graphite impurities with formation of >C=O groups at C-sp3 diamond structure. Addition of Fe(III compounds to the electrolyte provoke formation of the anodic wave on cyclic voltammograms in the potential region which correlates with generation of ferrate(VI. It is concluded that the direct electrochemical synthesis of Fe(VI at the borondopeddiamond anode is possible because of the less positive potential of ferrate(VIFeO2-4 formation in respect to the potential of oxygen evolution reaction. Presence of ferrate(VI in electrolyte, formed after anodic polarization of boron electrode in 10 M KOH electrolyte saturated with Fe(III at + 0.9 V against Hg|HgO electrode, has been proven by UV-VIS spectrometry.

A novel electrochemical approach to modifying aqueous solution pH in the vicinity of a detector electrode in order to optimize the electrochemical measurement signal is described. A ring disk electrode was employed where electrochemical decomposition of water on the ring was used to generate a flux of protons which adjusts the local pH controllably and quantifiably at the disk. Borondopeddiamond (BDD) functioned as the electrode material given the stability of this electrode surface especially when applying high potentials (to electrolyze water) for significant periods of time. A pH sensitive iridium oxide electrode electrodeposited on the disk electrode demonstrated that applied positive currents on the BDD ring, up to +50 μA, resulted in a local pH decrease of over 4 orders of magnitude, which remained stable over the measurement time of 600 s. pH generation experiments were found to be in close agreement with finite element simulations. The dual electrode arrangement was used to significantly improve the stripping peak signature for Hg in close to neutral conditions by the generation of pH = 2.0, locally. With the ability to create a localized pH change electrochemically in the vicinity of the detector electrode, this system could provide a simple method for optimized analysis at the source, e.g., river and sea waters.

The electrochemical degradation of saturated solutions of herbicides 4-chloro-2-methylphenoxyacetic acid, 2-(4-chlorophenoxy)-2-methylpropionic acid and 2-(4-chloro-2-methylphenoxy)propionic acid in 1 M HClO 4 on a boron-dopeddiamond (BDD) thin film anode has been studied by chronoamperometry, cyclic voltammetry and bulk electrolysis. At low anodic potentials polymeric products are formed causing the fouling and deactivation of BDD. This is reactivated at high potentials when water decomposes producing hydroxyl radical as strong oxidant of organics. Electrolyses in a batch recirculation system at constant current density ≥8 mA cm -2 yielded overall decontamination of all saturated solution. The effect of current density and herbicide concentration on the degradation rate of each compound, the specific charge required for its total mineralization and instantaneous current efficiency have been investigated. Experimental results have been compared with those predicted by a theoretical model based on a fast anodic oxidation of initial herbicides, showing that at 30 mA cm -2 their degradation processes are completely controlled by mass transfer. Kinetic analysis of the change of herbicide concentration with time during electrolysis, determined by high-performance liquid chromatography, revealed that all compounds follow a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids have been identified using this technique and a general pathway for the electrochemical incineration of all herbicides on BDD is proposed

Highlights: • Synthetic borondopeddiamond films were grown by hot filament chemical vapor deposition. • We characterized the films by hall effects as a function of temperature and magnetic field. • The resistivity was investigated. • The conduction mechanism was dominated by variable range hopping (VRH). - Abstract: The influence of doping level in the electronic conductivity and resistivity properties of synthetic diamond films grown by hot filament chemical vapor deposition (HFCVD) was investigated. Eight different doping level concentrations varied from 500 to 30,000 ppm were considered. The polycrystalline morphology observed by scanning electron microscopy and Raman spectra was strongly affected by the addition of boron. The electric characterization by Hall effect as a function of temperature and magnetic field showed that at sufficiently low temperatures, electrical conduction is dominated by variable range hopping (VRH) conducting process. The resistivity was also investigated by temperature-dependent transport measurements in order to investigate the conduction mechanism in the doped samples. The samples exhibited the VRH (m = 1/4) mechanism in the temperature range from 77 to 300 K. The interface between metal, and our HFCVD diamond was also investigated for the lower doped samples.

We report on a biosensor for organophosphate pesticides (OPs) by exploiting their inhibitory effect on the activity of acetylcholinesterase (AChE). A boron-dopeddiamond (BDD) electrode was modified with a nanocomposite prepared from carbon spheres (CSs; with an average diameter of 500 nm) that were synthesized from resorcinol and formaldehyde, and then were coated with gold nanoparticles (AuNPs) by chemically growing them of the CSs. Compared to a bare BDD electrode, the electron transfer resistance is lower on this new electrode. Compared to an electrode without Au-NPs, the peak potential is negatively shifted by 42 mV, and the peak current is increased by 55 %. This is ascribed to the larger surface in the AuNP-CS nanocomposite which improves the adsorption of AChE, enhances its activity, and facilitates electrocatalysis. Under optimum conditions, the inhibitory effect of chlorpyrifos is linearly related to the negative log of its concentration in the 10−11 to 10−7 M range, with a detection limit of 1.3 × 10 −13 M. For methyl parathion, the inhibition effect is linear in the 10 −12 to 10 −6 M range, and the detection limit is 4.9 × 10 −13 M. The biosensor exhibits good precision and acceptable operational and temporal stability. (author)

Oxidative protein surface mapping has become a powerful approach for measuring the solvent accessibility of folded protein structures. A variety of techniques exist for generating the key reagent – hydroxyl radicals – for these measurements; however, these approaches range significantly in their complexity and expense of operation. This research expands upon earlier work to enhance the controllability of boron-dopeddiamond (BDD) electrochemistry as an easily accessible tool for producing hydroxyl radicals in order to oxidize a range of intact proteins. Efforts to modulate oxidation level while minimizing the adsorption of protein to the electrode involved the use of relatively high flow rates to reduce protein residence time inside the electrochemical flow chamber. Additionally, a different cell activation approach using variable voltage to supply a controlled current allowed us to precisely tune the extent of oxidation in a protein-dependent manner. In order to gain perspective on the level of protein adsorption onto the electrode surface, studies were conducted to monitor protein concentration during electrolysis and gauge changes in the electrode surface between cell activation events. This report demonstrates the successful use of BDD electrochemistry for greater precision in generating a target number of oxidation events upon intact proteins. PMID:23210708

This work shows preliminary results on the electrochemical oxidation process (EOP) using boron-dopeddiamond (BDD) electrode for acidic yellow 36 oxidation, a common azo dye used in textile industry. The study is centred in the synergetic effect of ferrous ions and hydroxyl free radicals for improving discoloration of azo dye. The assays were carried out in a typical glass cell under potentiostatic conditions. On experimental conditions, the EOP was able to partially remove the dye from the reaction mixture. The reaction rate increased significantly by addition of Fe{sup 2+} (1 mM as ferrous sulphate) to the system and by (assumed) generation of ferrate ion [Fe(VI)] over BDD electrode. Ferrate is considered as a highly oxidizing reagent capable of removing the colorant from the reaction mixture, in synergistic action with the hydroxyl radicals produced on the BDD surface. Further increases in the Fe{sup 2+} concentration lead to depletion of the reaction rate probably due to the hydroxyl radical scavenging effect of Fe{sup 2+} excess in the system.

Electroanalysis was performed using a boron-dopeddiamond (BDD) electrode for the simultaneous detection of 2-heptyl-3-hydroxy-4-quinolone (PQS), 2-heptyl-4-hydroxyquinoline (HHQ) and pyocyanin (PYO). PQS and its precursor HHQ are two important signal molecules produced by Pseudomonas aeruginosa, while PYO is a redox active toxin involved in virulence and pathogenesis. This Gram-negative and opportunistic human pathogen is associated with a hospital-acquired infection particularly in patients with compromised immunity and is the primary cause of morbidity and mortality in cystic fibrosis (CF) patients. Early detection is crucial in the clinical management of this pathogen, with established infections entering a biofilm lifestyle that is refractory to conventional antibiotic therapies. Herein, a detection procedure was optimized and proven for the simultaneous detection of PYO, HHQ and PQS in standard mixtures, biological samples, and P. aeruginosa spiked CF sputum samples with remarkable sensitivity, down to nanomolar levels. Differential pulse voltammetry (DPV) scans were also applicable for monitoring the production of PYO, HHQ and PQS in P. aeruginosa PA14 over 8 h of cultivation. The simultaneous detection of these three compounds represents a molecular signature specific to this pathogen.

A novel paper-based analytical device (PAD) coupled with a silver nanoparticle-modified boron-dopeddiamond (AgNP/BDD) electrode was first developed as a cholesterol sensor. The AgNP/BDD electrode was used as working electrode after modification by AgNPs using an electrodeposition method. Wax printing was used to define the hydrophilic and hydrophobic areas on filter paper, and then counter and reference electrodes were fabricated on the hydrophilic area by screen-printing in house. For the amperometric detection, cholesterol and cholesterol oxidase (ChOx) were directly drop-cast onto the hydrophilic area, and H{sub 2}O{sub 2} produced from the enzymatic reaction was monitored. The fabricated device demonstrated a good linearity (0.39 mg dL{sup −1} to 270.69 mg dL{sup −1}), low detection limit (0.25 mg dL{sup −1}), and high sensitivity (49.61 μA mM{sup −1} cm{sup −2}). The precision value for ten replicates was 3.76% RSD for 1 mM H{sub 2}O{sub 2}. In addition, this biosensor exhibited very high selectivity for cholesterol detection and excellent recoveries for bovine serum analysis (in the range of 99.6–100.8%). The results showed that this new sensing platform will be an alternative tool for cholesterol detection in routine diagnosis and offers the advantages of low sample/reagent consumption, low cost, portability, and short analysis time. - Highlights: • Novel PAD coupled with AgNP/BDDE for cholesterol determination was developed. • Wide linear range, low detection limit and high selectivity were achieved. • This sensor was successfully applied for cholesterol determination in bovine serum. • This platform offers the advantages of low sample/reagent consumption and low cost.

Highlights: • BDD electrodes use an electrochemical pretreatment (anodic and/or cathodic) to restore their original characteristics and promote the reproduction of previous voltammograms; • Automatic system can carefully reproduce the electrochemical pretreatment of BDD electrode quickly and efficiently; • Open source platform “Arduino” can be used to developed a labmade apparatus to control a BDD electrode pretreatment system for analytical purposes; • The main advantages of this labmade apparatus are: low supporting electrolyte consumption (20 mL), a total time for each pretreatment of 80 seconds and an average cost of production below US$ 200. - Abstract: Every day, new electroanalytical methodologies are developed to supplant the established spectrometric and chromatographic methods due to their versatility, low cost and ability to perform measurements without sample treatment. Electroanalytical techniques have provided an alternative to quantify substances due to the direct relationship between the analyte concentration and some electrical property of the system. However, this ratio between the concentration and peak current is valid only if the electrochemically active area of the working electrode is constant in each electrochemical test. For years, classic polarography ensured the reproducibility of the mercury electrode surface due to its liquid state at room temperature. However, this metal has a high toxicity, driving the search for new inert materials for their replacement, most notably boron-dopeddiamond (BDD) electrodes. This electrode material has, among other attractive advantages for electroanalysis, a potential range higher than that of the mercury working electrode under the same conditions. Solid electrodes are, in general, polished to promote the reproducibility of their electrochemical performance. For BDD, the use of an electrochemical pretreatment (anodic and/or cathodic) has been sufficient to restore their original

Using square-wave voltammetry coupled to the boron-dopeddiamondelectrode (BDDE), it was possible to develop an analytical methodology for identification and quantification of diclofenac (DCL) in tablets and synthetic urine. The electroanalytical procedure was validated, with results being statistically equal to those obtained by chromatographic standard method, showing linear range of 4.94 × 10(-7) to 4.43 × 10(-6) mol L(-1), detection limit of 1.15 × 10(-7) mol L(-1), quantification limit of 3.85 × 10(-7) mol L(-1), repeatability of 3.05% (n = 10), and reproducibility of 1.27% (n = 5). The association of electrochemical techniques with UV-vis spectroscopy, computational simulations and HPLC-ESI/HRMS led us to conclude that the electrooxidation of DCL on the BDDE involved two electrons and two protons, where the products are colorful and easily hydrolyzable dimers. Density functional theory calculations allowed to evaluate the stability of dimers A, B, and C, suggesting dimer C was more stable than the other two proposed structures, ca. 4 kcal mol(-1). The comparison of the dimers stabilities with the stabilities of the molecular ions observed in the MS, the compounds that showed retention time (RT) of 15.53, 21.44, and 22.39 min were identified as the dimers B, C, and A, respectively. Corroborating the observed chromatographic profile, dimer B had a dipole moment almost twice higher than that of dimers A and C. As expected, dimer B has really shorter RT than dimers A and C. The majority dimer was the A (71%) and the C (19.8%) should be the minority dimer. However, the minority was the dimer B, which was formed in the proportion of 9.2%. This inversion between the formation proportion of dimer B and dimer C can be explained by preferential conformation of the intermediaries (cation-radicals) on the surface.

Highlights: ► Novel electrochemical sensor for the determination of codeine is presented. ► Codeine provided a single oxidation peak at +1.0 V vs. Ag/AgCl in BRBS at pH 7. ► Detection limit of 0.08 μM was achieved without electrode surface modification. ► Benefits of method: rapidity, low cost, low elaborateness and high repeatability. ► Possibility for drug quality control and drug analysis of biological samples. - Abstract: An unmodified boron-dopeddiamond film electrode was used for the first time as a sensitive and selective electrochemical sensor for the determination of codeine by the use of differential pulse voltammetry. Codeine provided a single well-defined oxidation peak at +1.0 V vs. Ag/AgCl in Britton-Robinson buffer solution at pH 7.0. Using the optimal differential pulse voltammetric conditions (modulation amplitude of 50 mV, modulation time of 40 ms and scan rate of 50 mV s −1 ), the detection limit of 0.08 μM, the linear response of peak current on codeine concentration in the range from 0.1 to 60 μM (R 2 = 0.998, n = 6) and relative standard deviation of 0.9% at 10 μM concentration level (n = 10) were achieved without any electrode surface modification. The influence of potential interfering agents on the current response was also studied and the results indicated that the proposed method was sufficiently selective. The method was successfully applied in the determination of codeine in real samples including pharmaceutical tablets and human urine with results similar to those declared by manufacturer and obtained by reference high-performance liquid chromatography method, respectively. The typical benefits of the method may be summarized as: rapidity (20 determinations per hour), sensitivity and selectivity, low cost and elaborateness, simplicity, wide linear concentration range, low detection limit and excellent repeatability. It might also represent the competitive alternative to the existing analytical methods in monitoring of

The electrochemical behavior of atorvastatin calcium at glassy carbon and boron-dopeddiamondelectrodes has been studied using voltammetric techniques. The possible mechanism of oxidation was discussed with model compounds. The dependence of the peak current and potentials on pH, concentration, scan rate and nature of the buffer were investigated for both electrodes. The oxidation of atorvastatin was irreversible and exhibited a diffusion-controlled fashion on the diamondelectrode. A linear response was obtained within the range of 9.65 x 10(-7) - 3.86 x 10(-5) M in 0.1 M H(2)SO(4) solution for both electrodes. The detection limits of a standard solution are estimated to be 2.11 x 10(-7) M with differential pulse voltammetry (DPV) and 2.05 x 10(-7)M with square wave voltammetry (SWV) for glassy carbon electrode, and 2.27 x 10(-7) M with DPV and 1.31 x 10(-7)M with SWV for diamondelectrodes in 0.1 M H(2)SO(4) solution. The repeatability of the methods was found good for both electrodes. The methods were fully validated and successfully applied to the high-throughput determination of the drug in tablets, human serum and human urine with good recoveries.

Biomolecule modified magnetic beads has been widely used in separation and sensing process. This study used streptavidin modified magnetic beads to immobilize biotin modified zanamivir. Biotin-streptavidin affinity facilitates immobilization of zanamivir on magnetic beads. Then interaction of zanamivir and neuraminidase was adopted as basic for enzyme detection. Detection of neuraminidase was performed at gold modified BDD using cyclic voltammetry technique. The measurement was carried out based on alteration of electrochemical signals of working electrode as neuraminidase response. The result showed that zanamivir was successfully immobilized on magnetic beads. The optimum amount of magnetic beads for zanamivir immobilization was 120 ug. Linear responses of neuraminidase were detected in concentration range of 0-15 mU. Detection limit (LOD) of measurement was 2.32 mU (R2 = 0.959) with precision as % RSD of 1.41%. Measurement of neuraminidase on magnetic beads could be also performed in the presence of mucin matrix. The linearity range was 0-8 mU with LOD of 0.64 mU (R2 = 0.950) and % RSD of 7.25%.

Graphical abstract: Display Omitted -- Highlights: • A bare boron-dopeddiamondelectrode was first used to determine fenfuram. • A sensitive voltammetric procedure for the determination of fenfuram was developed. • The sensor showed high sensitivity, selectivity, and wide linear range. • The procedure was successfully applied to detect fenfuram in real samples. • The effect of fenfuram on the uniform and pitting corrosion of steel was stated. -- Abstract: A simple, selective, and sensitive electroanalytical method for the determination of a novel fungicide, fenfuram (Fnf), on a bare boron-dopeddiamondelectrode (BDDE) using square-wave voltammetry (SWV) was developed. For the first time, the electrochemical oxidation of Fnf at BDDE at about 1.5 V vs. Ag/AgCl reference electrode in 0.35 mol L −1 sulfuric acid was investigated. To select the optimum experimental conditions, the effects of the supporting electrolyte, pH, frequency, amplitude, and step potential were studied. The developed method allowed the determination of Fnf in the concentration range of 2.4 × 10 −5 to 2.6 × 10 −4 mol L −1 (LOD = 6.3 × 10 −6 mol L −1 , LOQ = 2.1 × 10 −5 mol L −1 ). The validation of the method was carried out. The proposed procedure was successfully applied to determine Fnf in the spiked natural water samples collected from Polish rivers and in the spiked triticale seed samples by the standard addition method. To understand the Fnf electrode mechanism, the cyclic voltammetry (CV) technique was applied. The oxidation mechanism was also confirmed using mass spectrometry with the electrospray ionization (ESI-MS) technique. Using electrochemical techniques, the effect of Fnf on the corrosion properties of stainless steel which is used to produce agricultural tools was studied

Nanostructured diamond doped with boron was prepared using a hot-filament assisted chemical vapour deposition system fed with an ethyl alcohol, hydrogen and argon mixture. The reduction of the diamond grains to the nanoscale was produced by secondary nucleation and defects induced by argon and boron atoms via surface reactions during chemical vapour deposition. Raman measurements show that the samples are nanodiamonds embedded in a matrix of graphite and disordered carbon grains, while morphological investigations using field electron scanning microscopy show that the size of the grains ranges from 20 to 100 nm. The lowest threshold fields achieved were in the 1.6 to 2.4 V/μm range

Superconducting boron-dopeddiamond samples were synthesized with isotopes of 10B, 11B, 13C and 12C. We claim the presence of a carbon isotope effect on the superconducting transition temperature, which supports the ‘diamond-carbon’-related nature of superconductivity and the importance of the electron–phonon interaction as the mechanism of superconductivity in diamond. Isotope substitution permits us to relate almost all bands in the Raman spectra of heavily boron-dopeddiamond to the vibrat...

Electrochemical oxidation using a boron-dopeddiamond (BDD) anode is being investigated as a possible method for treating radiologically-contaminated oils. It has the potential to oxidise oils to carbon dioxide and water, and it would be particularly beneficial for oils contaminated with plutonium. It was found that simultaneous application of sonication and electro-oxidation produced and maintained an oil emulsion, so enabling its oxidation. This treatment was shown to be effective with 3 different oils: an unused hydraulic oil, an unused vacuum pump oil and a waste used machine tool oil, although the addition of a small amount of surfactant was required for the effective emulsification and oxidation of the vacuum pump oil. Essentially complete oxidation of the hydraulic oil in the absence of other organic material was demonstrated. The rate of oxidation appeared to be limited by the applied current when the concentration of oil was high and the current was low. Similarly, it was limited by the oil concentration when the concentration of oil was low and the current was relatively high. The required scale-up from a laboratory electrochemical cell is estimated to be 10,000 fold, which could entail a cell with a total BDD surface area of 3 m 2 , drawing a current of about 2000 A. It is anticipated that it should be possible to minimise the size of the cell by optimisation during the design of the prototype equipment. (authors)

Anodic oxidation of 4,6-dinitro-o-cresol (DNOC) has been studied in a cell of 100 ml with a boron-dopeddiamond anode and a graphite cathode, both of 3-cm 2 area. Solutions containing up to approximately 240 mg l -1 of compound in the pH range 2.0-12.0 have been treated at 100, 300 and 450 mA between 15 and 50 deg C. Total mineralization is always achieved due to the great amount of hydroxyl radical (·OH) produced as oxidant on the anode surface. Total organic carbon is more rapidly removed in acid medium, being the optimum pH 3.0. The degradation rate increases when temperature, current and DNOC concentration increase. However, at 100 mA depollution becomes more effective from 71 mg l -1 of initial pollutant. A pseudo first-order kinetics for DNOC decay is always found by reversed-phase chromatography, with a rate constant practically independent of pH, as expected if the same electroactive species is oxidized in all media. Ion-exclusion chromatography allowed the detection of oxalic acid as the ultimate carboxylic acid. The mineralization process leads to the complete release of NO 3 - ions from the destruction of nitroderivative intermediates. These products are oxidized simultaneously with accumulated oxalic acid up to the end of electrolyses. Comparative treatment of the same solutions with a Pt anode yields a quite poor depollution because of the generation of much lower amounts of reactive ·OH on its surface

Field emission properties of hot filament chemical vapor deposited borondoped polycrystalline diamond have been studied. Doping level (N B ) of different samples has been varied by the B/C concentration in the gas feed during the growth process and doping saturation has been observed for high B/C ratios. Threshold field (E th ) for electron emission as function of B/C concentration has been measured, and the influences of grain boundaries, doping level and surface morphology on field emission properties have been investigated. Carrier transport through conductive grains and local emission properties of surface sites have been figured out to be two independent limiting effects in respect of field emission. Emitter current densities of 500 nA cm -2 were obtained using electric fields less than 8 V/μm

Thin borondopeddiamond (BDD) film is deposited from trimethyl borate/acetone/hydrogen mixture on Co-cemented tungsten carbide (WC-Co) micro drills by using the hot filament chemical vapor deposition (HFCVD) technique. The boron peak on Raman spectrum confirms the boron incorporation in diamond film. This film is used as an interlayer for subsequent CVD of micro-crystalline diamond (MCD) film. The Rockwell indentation test shows that borondoping could effectively improve the adhesive streng...

Industrial wastewater containing non-biodegradable organic pollutants consists of highly toxic effluents whose treatment is necessary due to environmental and economical restrictions. In order to treat these effluents, an electrochemical process using a dimensionally stable anode (DSA Registered-Sign ) and boron-dopeddiamond (BDD) electrode was studied. The performance of these electrodes for COD removal from aqueous phenol solution was evaluated in the absence and presence of different chloride concentrations. The results showed that DSA Registered-Sign could be successfully used to remove COD when high chloride concentration (3035 mg L{sup -1}Cl{sup -}) and mild current density are employed (50 mA cm{sup -2}). On the other hand, the presence of chloride did not have the same significant effect on the COD depletion rate using BDD; however, under mild conditions (50 mA cm{sup -2}, 0.190 m s{sup -1}), the addition of 607 mg L{sup -1} Cl{sup -} improved the COD removal by approximately 52% after 8 hours of electrolysis. The effect of current density (i) and flow velocity (v) were also studied, and it was verified that they have an important role on the process performance, especially when DSA Registered-Sign is used. (author)

The development and validation of a multidimensional HPLC method using an on-line clean-up column coupled with amperometric detection employing a boron-dopeddiamond (BDD) electrode for the simultaneous determination of sulfamethoxazole (SMX) and trimethoprim (TMP) in bovine milk are presented. Aliquots of pre-prepared skim-milk samples were directly injected into a RAM octyl-BSA column in order to remove proteins that otherwise would interfere with milk analysis. After exclusion of the milk proteins, SMX and TMP were transferred to the analytical column (an octyl column) and the separation of the compounds from one another and from other endogenous milk components was achieved. SMX and TMP were detected amperometrically at 1.25 V vs. Ag/AgCl (3.0 mol L{sup -1} KCl). Results with good linearity in the concentration ranges 50-800 and 25-400 {mu}g L{sup -1} for SMX and TMP, respectively, were obtained and no fouling of the BDD electrode was observed within the experimental period of several hours. The intra- and inter-assay coefficients of variation were less than 10% for both drugs and the obtained LOD values for SMX and TMP were 25.0 and 15.0 {mu}g L{sup -1}, respectively.

Fabrication processes of thin boron-doped nanocrystalline diamond (B-NCD) films on silicon-based micro- and nano-electromechanical structures have been investigated. B-NCD films were deposited using microwave plasma assisted chemical vapour deposition method. The variation in B-NCD morphology, structure and optical parameters was particularly investigated. The use of truncated cone-shaped substrate holder enabled to grow thin fully encapsulated nanocrystalline diamond film with a thickness of approx. 60 nm and RMS roughness of 17 nm. Raman spectra present the typical boron-doped nanocrystalline diamond line recorded at 1148 cm-1. Moreover, the change in mechanical parameters of silicon cantilevers over-coated with boron-dopeddiamond films was investigated with laser vibrometer. The increase of resonance to frequency of over-coated cantilever is attributed to the change in spring constant caused by B-NCD coating. Topography and electrical parameters of boron-dopeddiamond films were investigated by tapping mode AFM and electrical mode of AFM-Kelvin probe force microscopy (KPFM). The crystallite-grain size was recorded at 153 and 238 nm for boron-doped film and undoped, respectively. Based on the contact potential difference data from the KPFM measurements, the work function of diamond layers was estimated. For the undoped diamond films, average CPD of 650 mV and for boron-doped layer 155 mV were achieved. Based on CPD values, the values of work functions were calculated as 4.65 and 5.15 eV for doped and undoped diamond film, respectively. Borondoping increases the carrier density and the conductivity of the material and, consequently, the Fermi level.

Since the fabrication of the first diamondelectrode in the mid 1980s, repid progress has been made on the development and application of this new type of electrode material. Boron-dopeddiamond (BDD) electrodes exhibit outstanding properties compared to oxygen-containing sp2 carbon electrodes. These properties make BDD electrodes an ideal choice for use in complex samples. In recent years, BDD microelectrodes have been applied to in vitro and in vivo measurements of biological molecules in animals, tissues and cells. This review will summarize recent progress in the development and applications of BDD electrodes in bio-sensing and in vitro measurements of biomolecules. In the first section, the methods for BDD nanocrystalline diamond film deposition and BDD microelectrodes preparation are described. This is followed by a description and discussion of several approaches for characterization of the BDD electrode surface structure, morphology, and electrochemical activity. Further, application of BDD microelectrodes for use in the in vitro analysis of norepinephrine (NE), serotonin (5-HT), nitric oxide (NO), histamine, and adenosine from tissues are summarized and finally some of the remaining challenges are discussed. PMID:21196394

Full Text Available With the rise of antibiotic resistance of pathogenic bacteria there is an increased demand for monitoring the functionality of bacteria membranes, the disruption of which can be induced by peptide-lipid interactions. In this work we attempt to construct and disrupt supported lipid membranes (SLB on borondoped nanocrystalline diamond (B-NCD. Electrochemical Impedance Spectroscopy (EIS was used to study in situ changes related to lipid membrane formation and disruption by peptide-induced interactions. The observed impedance changes were minimal for oxidized B-NCD samples, but were still detectable in the low frequency part of the spectra. The sensitivity for the detection of membrane formation and disruption was significantly higher for hydrogenated B-NCD surfaces. Data modeling indicates large changes in the electrical charge when an electrical double layer is formed at the B-NCD/SLB interface, governed by ion absorption. By contrast, for oxidized B-NCD surfaces, these changes are negligible indicating little or no change in the surface band bending profile.

Highlights: • Front and back side SIMS analysis of delta-layer boron-doped is a first for diamond. • Combination of front and back side depth profiling improves delta-layer analyses. • Sharp interfaces are evidenced on both sides of the delta-layer boron-dopeddiamond. • The growth of delta-layer borondopeddiamond is now well controlled. - Abstract: Nowadays the availability of very thin diamond layers in the range of nanometers as well as the possibility to characterize such delta-layer structures are required for the field of photonics and spintronics, but also for the development of next generation high power devices involving borondoping. The fabrication of diamond structures with abrupt interfaces such as superlattices and quantum wells has been recently improved. A very accurate characterization is then essential even though the analysis of such structures is arduous and challenging. SIMS analyses are commonly used to obtain depth profiles of dopants. However, below 10 nm in thickness, SIMS induced ion mixing effects which are no longer negligible. Then the raw SIMS profile might differ from the real dopant profile. In this study, we have analyzed a diamond structure containing a thin boron epilayer, especially synthesized to achieve SIMS analysis on both sides and to overcome the effects of ion mixing. We evidence the ion mixing induced by primary ions. Such a structure is a delta diamond layer, comparable to classical boron-doped delta-layer in silicon. Our results show that the growth of boron-doped delta-layer in diamond is now well controlled in terms of thickness and interfaces.

In this study, the residual stress of boron-dopeddiamond (BDD) films is investigated as a function of borondoping level using X-ray diffraction (XRD) analysis. Borondoping level is controlled from 1000ppm to 9000ppm by dissolving trimethyl borate into acetone. BDD films are deposited on silicon wafers using a bias-enhanced hot filament chemical vapor deposition (BE-HFCVD) system. Residual stress calculated by sin2 ψ method varies linearly from ‑2.4GPa to ‑1.1GPa with increasing borondoping level. On the BDD film of ‑1.75GPa, free standing BDD cantilevers are fabricated by photolithography and ICP-RIE processes, then tested by laser Doppler vibrometer (LDV). A cantilever with resonant frequency of 183KHz and Q factor of 261 in the air is fabricated.

Vertically aligned diamond nanowires with controlled geometrical properties like length and distance between wires were fabricated by use of nanodiamond particles as a hard mask and by use of reactive ion etching. The surface structure, electronic properties, and electrochemical functionalization of diamond nanowires were characterized by atomic force microscopy (AFM) and scanning tunneling microscopy (STM) as well as electrochemical techniques. AFM and STM experiments show that diamond nanowire etched for 10 s have wire-typed structures with 3-10 nm in length and with typically 11 nm spacing in between. The electrode active area of diamond nanowires is enhanced by a factor of 2. The functionalization of nanowire tips with nitrophenyl molecules is characterized by STM on clean and on nitrophenyl molecule-modified diamond nanowires. Tip-modified diamond nanowires are promising with respect to biosensor applications where controlled biomolecule bonding is required to improve chemical stability and sensing significantly.

Full Text Available Analysis of the induced stress on undoped and boron-dopeddiamond (BDD thin films by confocal Raman microscopy is performed in this study to investigate its correlation with sample chemical composition and the substrate used during fabrication. Knowledge of this nature is very important to the issue of long-term stability of BDD coated neurosurgical electrodes that will be used in fast-scan cyclic voltammetry, as potential occurrence of film delaminations and dislocations during their surgical implantation can have unwanted consequences for the reliability of BDD-based biosensing electrodes. To achieve a more uniform deposition of the films on cylindrically-shaped tungsten rods, substrate rotation was employed in a custom-built chemical vapor deposition reactor. In addition to visibly preferential boron incorporation into the diamond lattice and columnar growth, the results also reveal a direct correlation between regions of pure diamond and enhanced stress. Definite stress release throughout entire film thicknesses was found in the current Raman mapping images for higher amounts of boron addition. There is also a possible contribution to the high values of compressive stress from sp2 type carbon impurities, besides that of the expected lattice mismatch between film and substrate.

Highlights: ► Boron-dopeddiamond was used to degrade ethidium bromide. ► The process was optimized by a central composite rotatable design coupled with response surface methodology. ► Applied current is proved to be the most significant variable. ► A possible reaction sequence involving all the detected byproducts was proposed. - Abstract: The degradation of ethidium bromide (EtBr), a DNA intercalating pollutant, had been studied by anodic oxidation on boron-dopeddiamond (BDD) electrode under galvanostatic conditions. A central composite rotatable design coupled with response surface methodology was implemented to optimize the various operating parameters involved, among initial pH, flow rate, applied current and supporting electrolyte concentration, on the treatment efficiency; the latter was assessed in terms of color removal, COD removal, specific energy consumption and general current efficiency. Of the four parameters involved, applied current had a considerable effect on all the response factors. Optimum EtBr degradation was achieved by applying a current of 0.90 A, 9.0 mM Na 2 SO 4 , flow rate of 400 ml min −1 and pH 6.2 at 60 min of electrolysis, being reduced color by 80.2% and COD by 29.7%, with an energy consumption of 398.32 kW h (kg COD) −1 and a general current efficiency of 10.1%. Under these optimized conditions, EtBr decays followed pseudo first-order kinetics. Moreover, HPLC analysis of the BDD-treated solution allowed the detection of a number of reaction intermediates, and a possible reaction sequence involving all the detected byproducts was proposed for the electrochemical oxidation of EtBr on BDD anode.

To elucidate and to control polypyrrole (PPy) attachment to diamond we electrochemically grow PPy layers on hydrogen- and oxygen-terminated borondopeddiamonds (BDD). Atomic force microscopy (AFM) shows that the PPy layers have similar morphology (15 nm features) and thickness (> 5 nm) on H- and O-BDD. To resolve type of PPy-diamond bonding, scanning electron microscopy (SEM) is used to compare intensity of secondary electron emission from original BDD regions and regions where PPy was grown...

Superconducting boron-dopeddiamond samples were synthesized with isotopes of 10 B, 11 B, 13 C and 12 C. We claim the presence of a carbon isotope effect on the superconducting transition temperature, which supports the 'diamond-carbon'-related nature of superconductivity and the importance of the electron-phonon interaction as the mechanism of superconductivity in diamond. Isotope substitution permits us to relate almost all bands in the Raman spectra of heavily boron-dopeddiamond to the vibrations of carbon atoms. The 500 cm -1 Raman band shifts with either carbon or boron isotope substitution and may be associated with vibrations of paired or clustered boron. The absence of a superconducting transition (down to 1.6 K) in diamonds synthesized in the Co-C-B system at 1900 K correlates with the small boron concentration deduced from lattice parameters.

Diamond-coated cutting tools are used primarily for machining non-ferrous materials such as aluminum-silicon alloys, copper alloys, fiber-reinforced polymers, green ceramics and graphite. Because the tool life of cemented carbide cutting tool is greatly improved by diamond coating, and typically more than 10 times of the tool life is obtained. However, research of boron-dopeddiamond (BDD) coating tool has not been fully researched yet. In this study, we have succeeded to make boron-doped microcrystalline and nanocrystalline diamond-coated Co-cemented tungsten carbide (WC-Co) inserts. Microcrystalline BDD thin film is deposited on WC-Co insert by using microwave plasma enhanced chemical vapor deposition (MPECVD) method. Scanning electron microscope (SEM) and Raman spectroscopy are used to characterize the as-deposited diamond films.1,2

High-quality p-type boron-doped IIb diamond large single crystals are successfully synthesized by the temperature gradient method in a china-type cubic anvil high-pressure apparatus at about 5.5 GPa and 1600 K. The morphologies and surface textures of the synthetic diamond crystals with different boron additive quantities are characterized by using an optical microscope and a scanning electron microscope respectively. The impurities of nitrogen and boron in diamonds are detected by micro Fourier transform infrared technique. The electrical properties including resistivities, Hall coefficients, Hall mobilities and carrier densities of the synthesized samples are measured by a four-point probe and the Hall effect method. The results show that large p-type boron-dopeddiamond single crystals with few nitrogen impurities have been synthesized. With the increase of quantity of additive boron, some high-index crystal faces such as {113} gradually disappear, and some stripes and triangle pits occur on the crystal surface. This work is helpful for the further research and application of boron-doped semiconductor diamond. (cross-disciplinary physics and related areas of science and technology)

Diclofenac is a common anti-inflammatory drug. Its electrochemical degradation at borondopeddiamondelectrode was investigated in aqueous solution. The degradation kinetics and the intermediate products were studied. Results showed that electro-oxidation was effective in inducing the degradation of diclofenac with 30 mg/L initial concentration, ensuring a mineralization degree of 72% after a 4 h treatment with the applied bias potential of 4.0 V. The effects of applied bias potential and addition of NaCl on diclofenac degradation were investigated. Different degradation mechanisms of diclofenac were involved at various applied bias potentials. With the addition of NaCl, some chlorination intermediates including dichlorodiclofenac were identified, which lead to the total organic carbon increase compared with the electrolysis process without NaCl addition at the reaction initial period. The main intermediates including 2,6-dichlorobenzenamine, 2,5-dihydroxybenzyl alcohol, and benzoic acid are identified at the time of 2 h. 1-(2,6-Dichlorocyclohexa-2,4-dienyl)indolin-2-one were also identified. These intermediates disappeared gradually with the extension of reaction time. Small molecular acids were identified finally. Based on these results, a degradation pathway of diclofenac was proposed.

Diclofenac is a common anti-inflammatory drug. Its electrochemical degradation at borondopeddiamondelectrode was investigated in aqueous solution. The degradation kinetics and the intermediate products were studied. Results showed that electro-oxidation was effective in inducing the degradation of diclofenac with 30 mg/L initial concentration, ensuring a mineralization degree of 72% after a 4 h treatment with the applied bias potential of 4.0 V. The effects of applied bias potential and addition of NaCl on diclofenac degradation were investigated. Different degradation mechanisms of diclofenac were involved at various applied bias potentials. With the addition of NaCl, some chlorination intermediates including dichlorodiclofenac were identified, which lead to the total organic carbon increase compared with the electrolysis process without NaCl addition at the reaction initial period. The main intermediates including 2,6-dichlorobenzenamine, 2,5-dihydroxybenzyl alcohol, and benzoic acid are identified at the time of 2 h. 1-(2,6-Dichlorocyclohexa-2,4-dienyl)indolin-2-one were also identified. These intermediates disappeared gradually with the extension of reaction time. Small molecular acids were identified finally. Based on these results, a degradation pathway of diclofenac was proposed.

During this PhD project, the metal-insulator transition and superconductivity of highly boron-doped single crystal diamond and related materials have been investigated. The critical boron concentration n{sub c} for the metal-insulator transition was found to be the same as for the normal-superconductor transition. All metallic samples have been found to be superconducting and we were able to link the occurence of superconductivity to the proximity to the metal-insulator transition. For this purpose, a scaling law approach based on low temperature transport was proposed. Furthermore, we tried to study the nature of the superconductivity in highly borondoped single crystal diamond. Raman spectroscopy measurements on the isotopically substituted series suggest that the feature occuring at low wavenumbers ({approx} 500 cm{sup -1}) is the A1g vibrational mode associated with boron dimers. Usual Hall effect measurements yielded a puzzling situation in metallic boron-dopeddiamond samples, leading to carrier concentrations up to a factor 10 higher than the boron concentration determined by secondary ion mass spectroscopy (SIMS). The low temperature transport follows the one expected for a granular metal or insulator, depending on the interplay of intergranular and intragranular (tunneling) conductance. The metal-insulator transition takes place at a critical conductance g{sub c}. The granularity also influences significantly the superconducting properties by introducing the superconducting gap {delta} in the grain and Josephson coupling J between superconducting grains. A peak in magnetoresistance is observed which can be explained by superconducting fluctuations and the granularity of the system. Additionally we studied the low temperature transport of boron-doped Si samples grown by gas immersion laser doping, some of which yielded a superconducting transition at very low temperatures. Furthermore, preliminary results on the LO-phonon-plasmon coupling are shown for the

Full Text Available We have investigated the low-energy electronic state of boron-dopeddiamond thin film by the laser-excited photoemission spectroscopy. A clear Fermi-edge is observed for samples doped above the semiconductor–metal boundary, together with the characteristic structures at 150×n meV possibly due to the strong electron–lattice coupling effect. In addition, for the superconducting sample, we observed a shift of the leading edge below Tc indicative of a superconducting gap opening. We discuss the electron–lattice coupling and the superconductivity in doped diamond.

The electrochemical oxidation of acid black 210 dye (AB-210) on the boron-dopeddiamond (BDD) was investigated under different pH conditions. The best performance for the AB-210 oxidation occurred in alkaline phosphate solution. This is probably due to oxidizing agents such as phosphate radicals and peroxodiphosphate ions, which can be electrochemically produced with good yields on the BDD anode, mainly in alkaline solution. Under this condition, the COD (chemical oxygen demand) removal was higher than that obtained from the model proposed by Comninellis. Electrolyses performed in phosphate buffer and in the presence of chloride ions resulted in faster COD and color removals in acid and neutral solutions, but in alkaline phosphate solution, a better performance in terms of TOC removal was obtained in the absence of chloride. Moreover, organochloride compounds were detected in all electrolyses performed in the presence of chloride. The AB-210 electrooxidation on BDD using phosphate as supporting electrolyte proved to be interesting since oxidizing species generated from phosphate ions were able to completely degrade the dye without producing organochloride compounds.

This review presents a brief account concerning the production, characterization and evolution of the knowledge in the area of diamond and boron-dopeddiamond films. The most important methods used for the growth of these films, such as chemical vapor deposition and high pressure/high temperature systems, as well as the several kinds of reactors which can be employed are reviewed. However, larger emphasis is given to the CVD method. Morphological, structural and electric properties of these films, as well as their role in the performance of voltammetric electrodes for electrochemistry and electroanalytical chemistry are also discussed. (author)

Chemical vapor deposition (CVD) diamond films have attracted more attentions due to their excellent mechanical properties. Whereas as-fabricated traditional diamond films in the previous studies don't have enough adhesion or surface smoothness, which seriously impact their friction and wear performance, and thus limit their applications under extremely harsh conditions. A borondoped, undoped microcrystalline and fine grained composite diamond (BD-UM-FGCD) film is fabricated by a three-step method adopting hot filament CVD (HFCVD) method in the present study, presenting outstanding comprehensive performance, including the good adhesion between the substrate and the underlying borondopeddiamond (BDD) layer, the extremely high hardness of the middle undoped microcrystalline diamond (UMCD) layer, as well as the low surface roughness and favorable polished convenience of the surface fine grained diamond (FGD) layer. The friction and wear behavior of this composite film sliding against low-carbon steel and silicon nitride balls are studied on a ball-on-plate rotational friction tester. Besides, its wear rate is further evaluated under a severer condition using an inner-hole polishing apparatus, with low-carbon steel wire as the counterpart. The test results show that the BD-UM-FGCD film performs very small friction coefficient and great friction behavior owing to its high surface smoothness, and meanwhile it also has excellent wear resistance because of the relatively high hardness of the surface FGD film and the extremely high hardness of the middle UMCD film. Moreover, under the industrial conditions for producing low-carbon steel wires, this composite film can sufficiently prolong the working lifetime of the drawing dies and improve their application effects. This research develops a novel composite diamond films owning great comprehensive properties, which have great potentials as protecting coatings on working surfaces of the wear-resistant and anti

Full Text Available We have performed soft X-ray angle-resolved photoemission spectroscopy (SXARPES of microwave plasma-assisted chemical vapor deposition diamond films with different B concentrations in order to study the origin of the metallic behavior of superconducting diamond. SXARPES results clearly show valence band dispersions with a bandwidth of ~23 eV and with a top of the valence band at gamma point in the Brillouin zone, which are consistent with the calculated valence band dispersions of pure diamond. Boron concentration-dependent band dispersions near the Fermi level (EF exhibit a systematic shift of EF, indicating depopulation of electrons due to hole doping. These SXARPES results indicate that diamond bands retain for heavy borondoping and holes in the diamond band are responsible for the metallic states leading to superconductivity at low temperature. A high-resolution photoemission spectroscopy spectrum near EF of a heavily boron-dopeddiamond superconductor is also presented.

Borondoped ultrananocrystalline diamond (B-UNCD) growth was studied on modified reticulated vitreous carbon (RVC) produced from poly(furfuryl alcohol) (PFA) resin with sodium hydroxide additions at two different heat treatment temperatures. The different amounts of NaOH in PFA (up to reaching pH values of around 3, 5, 7, and 9) aimed to neutralize the acid catalyst and to increase the PFA storage life. Besides, this procedure was responsible for increasing the oxygen content of RVC samples. Thus, the effect of carbon and oxygen coming from the substrates in addition to their different graphitization indexes on diamond morphology, grain size, preferential growth and borondoping level were investigated by FEG-SEM, x-ray diffraction and Raman spectroscopy. Therefore, B-UNCD films were successfully grown on RVC with pH values of 3, 5, 7, and 9 heat treated at 1000 and 1700 °C. Nonetheless, the higher oxygen amount during B-UNCD growth for samples with pH 7 and 9 heat treated at 1000 °C was responsible for the RVC surface etching and the decrease in the boron concentration of such samples. The cross section images showed that B-UNCD infiltrated at around 0.9 mm in depth of RVC samples while carbon nanowalls were observed mainly on RVC samples heat treated at 1000 °C for all pH range studied.

Thin borondopeddiamond (BDD) film is deposited from trimethyl borate/acetone/hydrogen mixture on Co-cemented tungsten carbide (WC-Co) micro drills by using the hot filament chemical vapor deposition (HFCVD) technique. The boron peak on Raman spectrum confirms the boron incorporation in diamond film. This film is used as an interlayer for subsequent CVD of micro-crystalline diamond (MCD) film. The Rockwell indentation test shows that borondoping could effectively improve the adhesive strength on substrate of as deposited thin diamond films. Dry drilling of graphite is chosen to check the multilayer (BDD + MCD) film performance. For the sake of comparison, machining tests are also carried out under identical conditions using BDD and MCD coated micro drills with no interlayer. The wear mechanism of the tools has been identified and correlated with the criterion used to evaluate the tool life. The results show that the multilayer (BDD + MCD) coated micro drill exhibits the longest tool life. Therefore, thin BDD interlayer is proved to be a new viable alternative and a suitable option for adherent diamond coatings on micro cutting tools.

Full Text Available Thin borondopeddiamond (BDD film is deposited from trimethyl borate/acetone/hydrogen mixture on Co-cemented tungsten carbide (WC-Co micro drills by using the hot filament chemical vapor deposition (HFCVD technique. The boron peak on Raman spectrum confirms the boron incorporation in diamond film. This film is used as an interlayer for subsequent CVD of micro-crystalline diamond (MCD film. The Rockwell indentation test shows that borondoping could effectively improve the adhesive strength on substrate of as deposited thin diamond films. Dry drilling of graphite is chosen to check the multilayer (BDD + MCD film performance. For the sake of comparison, machining tests are also carried out under identical conditions using BDD and MCD coated micro drills with no interlayer. The wear mechanism of the tools has been identified and correlated with the criterion used to evaluate the tool life. The results show that the multilayer (BDD + MCD coated micro drill exhibits the longest tool life. Therefore, thin BDD interlayer is proved to be a new viable alternative and a suitable option for adherent diamond coatings on micro cutting tools.

Thin borondopeddiamond (BDD) film is deposited from trimethyl borate/acetone/hydrogen mixture on Co-cemented tungsten carbide (WC-Co) micro drills by using the hot filament chemical vapor deposition (HFCVD) technique. The boron peak on Raman spectrum confirms the boron incorporation in diamond film. This film is used as an interlayer for subsequent CVD of micro-crystalline diamond (MCD) film. The Rockwell indentation test shows that borondoping could effectively improve the adhesive strength on substrate of as deposited thin diamond films. Dry drilling of graphite is chosen to check the multilayer (BDD + MCD) film performance. For the sake of comparison, machining tests are also carried out under identical conditions using BDD and MCD coated micro drills with no interlayer. The wear mechanism of the tools has been identified and correlated with the criterion used to evaluate the tool life. The results show that the multilayer (BDD + MCD) coated micro drill exhibits the longest tool life. Therefore, thin BDD interlayer is proved to be a new viable alternative and a suitable option for adherent diamond coatings on micro cutting tools. PMID:28811426

The outstanding properties of diamond make it a very attractive material for use in many potential applications. In particular, the superior electrochemical properties of highly boron-doped conductive diamond films, prepared by the chemical vapor deposition (CVD) process, have received attention from electrochemists. This paper reports several diversified applications of boron-dopeddiamondelectrodes; highly sensitive and interference-free microfiber electrodes with over-oxidized polypyrrole modification, integrated electrochemical detector for microchip capillary electrophoresis (CE), and smoothing treatments of micro-polycrystalline surface. Studies have been made of the electrochemical properties of each system and their application in electroanalysis is discussed

We quantitatively investigate the biocompatibility of chemical vapour deposited (CVD) nanocrystalline diamond (NCD) after the inclusion of boron, with and without nanostructuring. The nanostructuring method involves a novel approach of growing NCD over carbon nanotubes (CNTs) that act as a 3D scaffold. This nanostructuring of BNCD leads to a material with increased capacitance, and this along with wide electrochemical window makes BNCD an ideal material for neural interface applications, and thus it is essential that their biocompatibility is investigated. Biocompatibility was assessed by observing the interaction of human neural stem cells (hNSCs) with a variety of NCD substrates including un-doped ones, and NCD doped with boron, which are both planar, and nanostructured. hNSCs were chosen due to their sensitivity, and various methods including cell population and confluency were used to quantify biocompatibility. Boron inclusion into NCD film was shown to have no observable effect on hNSC attachment, proliferation and viability. Furthermore, the biocompatibility of nanostructured boron-doped NCD is increased upon nanostructuring, potentially due to the increased surface area. Diamond is an attractive material for supporting the attachment and development of cells as it can show exceptional biocompatibility. When boron is used as a dopant within diamond it becomes a p-type semiconductor, and at high concentrations the diamond becomes quasi-metallic, offering the prospect of a direct electrical device-cell interfacing system.

Highlights: · Diamond anode enables total abatement of a real textile effluent COD with low energy consumption. · Use of diamond anode enables excellent decolorization rate of effluent in the presence of Cl - ions. · Diamond anode might be an excellent option for electrochemical treatment of real textile effluents. · PbO 2 anode, due to low cost and easiness of preparation, may be an option to decolorize the effluents. - Abstract: Constant current electrolyses are carried out in a filter-press reactor using a boron-dopeddiamond (Nb/BDD) or a Ti-Pt/β-PbO 2 anode, varying current density (j) and temperature. The degradation of the real textile effluent is followed by its decolorization and chemical oxygen demand (COD) abatement. The effect of adding NaCl (1.5 g L -1 ) on the degradation of the effluent is also investigated. The Nb/BDD anode yields much higher decolorization (attaining the DFZ limit) and COD-abatement rates than the Ti-Pt/β-PbO 2 anode, at any experimental condition. The best conditions are j = 5 mA cm -2 and 55 o C, for the system's optimized hydrodynamic conditions. The addition of chloride ions significantly increases the decolorization rate; thus a decrease of more than 90% of the effluent relative absorbance is attained using an applied electric charge per unit volume of the electrolyzed effluent (Q ap ) of only about 2 kA h m -3 . Practically total abatement of the effluent COD is attained with the Nb/BDD anode using a Q ap value of only 7 kA h m -3 , with an energy consumption of about 30 kW h m -3 . This result allows to conclude that the Nb/BDD electrode might be an excellent option for the remediation of textile effluents.

Porous borondopeddiamonds (BDDs) were obtained on foam nickel substrates with a porosity of 80%, 85%, 90% and 95% respectively by hot filament chemical vapor deposition (HFCVD) technology. Scanning electron microscopy (SEM) reveals that uniform and compact BDDs with a cauliflower-like morphology have covered the overall frame of the foam nickel substrates. Raman spectroscopy shows that the BDDs have a poor crystallinity due to heavily doping boron. X-ray photoelectron spectroscopy (XPS) analysis effectively demonstrates that boron atoms can be successfully incorporated into the crystal lattice of diamonds. Electrochemical measurements indicate that the oxygen reduction potential is unaffected by the specific surface area (SSA), and both the onset potential and the limiting diffusion current density are enhanced with increasing SSA. It is also found that the durability and methanol tolerance of the borondopeddiamond catalysts are attenuated as the increasing of SSA. The SSA of the catalyst is directly proportional to the oxygen reduction activity and inversely to the durability and methanol resistance. These results provide a reference to the application of porous borondopeddiamonds as potential cathodic catalysts for the oxygen reduction reaction in alkaline solution by adjusting the SSA.

The boron-dopeddiamond (BDD) powder consisting of 40-100 μm particles was synthesized at 5 GPa and 1500-1600 °C from a mixture of 50 wt% graphite and 50 wt% Ni-Mn catalyst with an addition of 1 wt% or 5 wt% boron powder. The size of crystal domains of doped and non-doped diamond was evaluated as a coherent scattering region by X-ray diffraction (XRD) and using small-angle neutron scattering (SANS), being ≥180 nm (XRD) and 100 nm (SANS). Magnetic impurities of NiMnx originating from the catalyst in the synthesis, which prevent superconductivity, were detected by magnetization measurements at 2-300 K. X-ray photoelectron spectroscopy, the temperature dependence of the resistivity, XRD, and Raman spectroscopy reveal that the concentration of electrically active boron is as high as (2±1)×1020 cm-3 (0.1 at%). To the best of our knowledge, this is the highest boron content for BDD synthesized in high-pressure high-temperature process with metal catalysts.

The growth of covalently bonded nitrophenyl layers on atomically smooth boron-doped single-crystalline diamond surfaces is characterized using cyclic voltammetric attachment and constant-potential grafting by electrochemical reduction of aryl diazonium salts. We apply atomic force microscopy (AFM) in contact mode to remove phenyl layers and measure phenyl layer thicknesses by oscillatory AFM. Angle-resolved X-ray photoelectron spectroscopy is applied to reveal the bonding arrangement of phenyl molecules, and transient current measurements during the grafting are used to investigate the dynamics of chemical bonding. Nitrophenyl groups at an initial stage of attachment grow three-dimensional (3D), forming layers of varying heights and densities. Layer thicknesses of up to 80 A are detected for cyclic voltammetry attachment after five cycles, whereas the layer becomes denser and only about 25 A thick in the case of constant-potential attachment. No monomolecular closed layer can be detected. The data are discussed taking into account established growth models. Redox systems such as Fe(CN)63-/4- and Ru(NH3)62+/3+ are used to probe the electrochemical barrier properties of nitrophenyl groups grafted onto diamond.

Work function of carbon electrodes is critical in obtaining high open-circuit voltage as well as high device performance for carbon-based perovskite solar cells. Herein, we propose a novel strategy to upshift work function of carbon electrode by incorporating boron atom into graphite lattice and employ it in printable hole-conductor-free mesoscopic perovskite solar cells. The high-work-function boron-doped carbon electrode facilitates hole extraction from perovskite as verified by photoluminescence. Meanwhile, the carbon electrode is endowed with an improved conductivity because of a higher graphitization carbon of boron-doped graphite. These advantages of the boron-doped carbon electrode result in a low charge transfer resistance at carbon/perovskite interface and an extended carrier recombination lifetime. Together with the merit of both high work function and conductivity, the power conversion efficiency of hole-conductor-free mesoscopic perovskite solar cells is increased from 12.4% for the pristine graphite electrode-based cells to 13.6% for the boron-doped graphite electrode-based cells with an enhanced open-circuit voltage and fill factor.

Graphical abstract: - Highlights: • Nature of electrode material decides the electrocatalytic mechanism followed. • Electrogenerated strong oxidants on BDD surface improve the color and organic load removal. • Chlorine active species act in solution cage oxidizing organic matter. - Abstract: The present study discusses the electrochemical degradation process of a textile dye, Novacron Yellow C-RG (NY), dissolved in synthetic wastewaters, via direct and indirect oxidation. Experiments were conducted using boron-dopeddiamond (BDD) and platinum supported on Ti (Pt/Ti) electrodes in the absence and presence of NaCl in the solution. The direct process for removing color is relatively similar for both anodes, while the electrochemical degradation is significantly accelerated by the presence of halogen salt in the solution. Interestingly, it does not depend on applied current density, but rather on NaCl concentration. Therefore, the electrochemical processes (direct/indirect) favor specific oxidation pathways depending on electrocatalytic material. Whereas, the Pt/Ti anode favors preferentially color removal by direct and indirect oxidation (100% of color removal) due to the fragmentation of the azo dye group; BDD electrode favors color and organic load removals in both processes (95% and up to 87%, respectively), due to the rupture of dye in different parts of its chemical structure. Parameters of removal efficiency and energy consumption for the electrochemical process were estimated. Finally, an explanation has been attempted for the role of halide, in relation with the oxygen evolution reaction, concomitant with the electrochemical incineration as well as electrocatalytic mechanisms, for each one of the electrodes used

A fluorine-terminated polycrystalline boron-dopeddiamond surface is successfully employed as a pH-insensitive SGFET (solution-gate field-effect transistor) for an all-solid-state pH sensor. The fluorinated polycrystalline boron-dopeddiamond (BDD) channel possesses a pH-insensitivity of less than 3mV/pH compared with a pH-sensitive oxygenated channel. With differential FET (field-effect transistor) sensing, a sensitivity of 27 mv/pH was obtained in the pH range of 2-10; therefore, it demonstrated excellent performance for an all-solid-state pH sensor with a pH-sensitive oxygen-terminated polycrystalline BDD SGFET and a platinum quasi-reference electrode, respectively.

The use of square-wave voltammetry in conjunction with a cathodic ally pre-treated diamondelectrode for the analytical determination of sodium cyclamate is described. The samples were analyzed as received in a 0.5 mol L{sup -1} H{sub 2}SO{sub 4} solution in the concentration range from 5.0 x 10{sup -5} mol L{sup -1} to 4.1 x. 10{sup -4} mol L{sup -1}, with a detection limit of 4.8 x 10{sup -6} mol L{sup -1}. The RSD was smaller than 1.2 % and the proposed method was applied with success in the determination of sodium cyclamate in several dietary products. (author)

Full Text Available The Cu/Pd bimetallic system electrodeposited on boron-dopeddiamond (BDD films for application, as electrode material in the electrochemical reduction of nitrate was studied. The electrochemical behavior of Cu, Pd, and Cu/Pd bimetallic system was evaluated by cyclic voltammetry. From these results, the formation of the Cu/Pd composite was verified. In addition, Cu with different phases and a Cu/Pd phase in the composite were obtained. Morphological analysis by scanning electron microscopy (SEM revealed a homogeneous distribution of Cu/Pd bimetallic particles with intermediary dimensions compared to those observed in Cu or Pd electrodeposits separately. These composites were tested as electrocatalysts for nitrate reduction in Britton-Robinson buffer solution (pH 9. Electrochemical measurements showed that composites with higher Cu content displayed the best electrocatalytic activity for nitrate reduction, and the Cu/Pd phase in the bimetallic system served to improve the Cu adherence on BDD electrode.

The removal efficiency of four commonly-used parabens by electrochemical advanced oxidation with boron-dopeddiamond anodes in two different aqueous matrices, namely ultrapure water and surface water from the Guadiana River, has been analyzed. Response surface methodology and a factorial, composite, central, orthogonal, and rotatable (FCCOR) statistical design of experiments have been used to optimize the process. The experimental results clearly show that the initial concentration of pollutants is the factor that influences the removal efficiency in a more remarkable manner in both aqueous matrices. As a rule, as the initial concentration of parabens increases, the removal efficiency decreases. The current density also affects the removal efficiency in a statistically significant manner in both aqueous matrices. In the water river aqueous matrix, a noticeable synergistic effect on the removal efficiency has been observed, probably due to the presence of chloride ions that increase the conductivity of the solution and contribute to the generation of strong secondary oxidant species such as chlorine or HClO/ClO - . The use of a statistical design of experiments made it possible to determine the optimal conditions necessary to achieve total removal of the four parabens in ultrapure and river water aqueous matrices.

Full Text Available We report on scanning tunneling microscopy/spectroscopy (STM/STS experiments on (1 1 1-oriented epitaxial films of heavily boron-dopeddiamond grown by using the microwave plasma-assisted chemical vapor deposition method. STM/STS measurements were performed by 3He-refrigerator based STM under ultra-high vacuum. The STM topography on the film surface shows a corrugation (with a typical size of ~1 μm and grain-like microstructures (~5–20 nm. The tunneling conductance spectra do not show large spatial dependence and superconductivity is observed independent of the surface structures. The tunneling spectra are analyzed by the Dynes function and the superconducting energy gap is estimated to be Δ=0.87 meV at T=0.47 K, corresponding to 2Δ/kBTc=3.7. The relatively large value of the broadening parameter Γ=0.38 meV is discussed in terms of the inelastic electron scattering processes.

Peroxynitrite is a potent nitroxidation agent and highly reactive metabolite, clinically correlated with a rich pathophysiology. Its sensitive and selective detection is challenging due to its high reactivity and short sub-second lifetime. Boron-dopeddiamond (BDD) microelectrodes have attracted interest because of their outstanding electroanalytical properties that include a wide working potential window and enhanced signal-to-noise ratio. Herein, we report on the modification of a BDD microelectrode with an electro-polymerized film of hemin and polyethylenedioxythiophene (PEDOT) for the purpose of selectively quantifying peroxynitrite. The nanostructured modified polymer layer was characterized by Raman spectroscopy and scanning electron microscopy (SEM). The electrochemical response to peroxynitrite was studied by voltammetry and time-based amperometry. The measured detection limit was 10 ± 0.5 nM (S/N = 3), the sensitivity was 4.5 ± 0.5 nA nM(-1) and the response time was 3.5 ± 1 s. The hemin-PEDOT BDD sensors exhibited a response variability of 5% or less (RSD). The stability of the sensors after a 20-day storage in 0.1 M PB (pH 7.4) at 4 °C was excellent as at least 93% of the initial response to 50 nM PON was maintained. The presence of PEDOT was correlated with a sensitivity increase.

A boron-doped carbon nanotube (BCNT)-modified glassy carbon (GC) electrode was constructed for the detection of L-cysteine (L-CySH). The electrochemical behavior of BCNTs in response to L-cysteine oxidation was investigated. The response current of L-CySH oxidation at the BCNT/GC electrode was obviously higher than that at the bare GC electrode or the CNT/GC electrode. This finding may be ascribed to the excellent electrochemical properties of the BCNT/GC electrode. Moreover, on the basis of this finding, a determination of L-CySH at the BCNT/GC electrode was carried out. The effects of pH, scan rate and interferents on the response of L-CySH oxidation were investigated. Under the optimum experimental conditions, the detection response for L-CySH on the BCNT/GC electrode was fast (within 7 s). It was found to be linear from 7.8 x 10 -7 to 2 x 10 -4 M (r = 0.998), with a high sensitivity of 25.3 ± 1.2 nA mM -1 and a low detection limit of 0.26 ± 0.01 μM. The BCNT/GC electrode exhibited high stability and good resistance against interference by other oxidizable amino acids (tryptophan and tyrosine)

Highlights: • Fabrication of low-cost photocathode by electrochemical method is described. • Boron-dopeddiamond is presented as catalyst support. • NiO nanoparticles on Cu{sub 2}O surface enhances photocurrent and electrode stability. • Synergy of metallic interaction between Cu and Ni leads to high efficiency. - Abstract: Herein, we report a novel photocathode for the water splitting reaction. The electrochemical deposition of Cu{sub 2}O particles on borondopeddiamond (BDD) electrodes and the subsequent decoration with NiO nanoparticles by a dip coating method to act as co-catalyst for hydrogen evolution reaction is described. The morphology analysis by scanning electron microscope (SEM) revealed that Cu{sub 2}O particles are cubic and decorated sporadically with NiO nanoparticles. X-ray photoelectron spectroscopy (XPS) confirmed the electronic interaction at the interface between Cu{sub 2}O and NiO through a binding energy shift of the main Cu 2p peak. The photoelectrochemical (PEC) performance of NiO-Cu{sub 2}O/BDD showed a much higher current density (−0.33 mA/cm{sup 2}) and photoconversion efficiency (0.28%) compared to the unmodified Cu{sub 2}O/BDD electrode, which are only −0.12 mA/cm{sup 2} and 0.06%, respectively. The enhancement in PEC performance is attributable to the synergy of NiO as an electron conduction mediator leading to the enhanced charge separation and transfer to the reaction interface for hydrogen evolution as evidenced by electrochemical impedance spectroscopy (EIS) and charge carrier density calculation. Stability tests showed that the NiO nanoparticles loading content on Cu{sub 2}O surface is a crucial parameter in this regard.

Full Text Available This work presents the construction and application of boron-dopeddiamond(BDD thin film electrode as sensor for the determination of three ÃŽÂ²-agonists, viz.salbutamol, terbutaline and clenbuterol. Although well-known as a chemically inertmaterial, BDD film however shows fouling in detection of these compounds using fixedpotentialmode amperometry. A suitable waveform for pulsed amperometric detection(PAD was developed and used to determine the agonist compounds. It was seen that thedeveloped PAD significantly refreshed the BDD surface for long-term detection in flowinjection analysis. Linear working ranges were 0.5-100 ÃŽÂ¼M, 1.0-100 ÃŽÂ¼M and 0.5-50 ÃŽÂ¼M forsalbutamol, terbutaline and clenbuterol, respectively. The developed PAD-BDD system wasapplied to successfully determine salbutamol and terbutaline in commercial pharmaceuticalproducts. The methods were validated with a capillary electrophoresis method.

Recently, electrochemical activation of sulfate ions to sulfate radical species and nonradically activated persulfate has been demonstrated at boron-dopeddiamond (BDD) anode, which enhanced the electrooxidation kinetics of several persistent contaminants. In this study, we investigated the transformation pathways of two X-ray contrast media (ICM), diatrizoate and iopromide, in electrooxidation at BDD anode using sulfate and inert nitrate anolyte. Sulfate anolyte yielded a seven-fold increase in apparent rate constants for ICM oxidation compared to inert nitrate anolyte, and a two-fold increase for the removal of organic carbon. Higher iodine release was observed in electrooxidation of diatrizoate compared to iopromide. In the case of diatrizoate, around 80% of deiodination efficiency was achieved in both anolytes. Deiodination efficiency of iopromide was somewhat lower in nitrate anolyte (≤75%) and significantly reduced in sulfate anolyte (≤46%) due to a larger steric hindrance of alkyl side chains. Moreover, a considerable lag phase of iopromide deiodination was observed in sulfate anolyte, indicating that initial oxidation reactions took place almost exclusively at the alkyl side chains. Several transformation products (TPs) of ICM were identified in electrooxidation in sulfate anolyte, and only three TPs in the case of nitrate anolyte. The main mechanistic steps in the oxidation of iopromide were H-abstraction and bond cleavage in the alkyl side chains. Diatrizoate was mainly transformed through oxidative cleavage of iodine substituent and inter-molecular cyclization. Two hydroxylamine derivatives of iopromide and a nitro-derivative of diatrizoate were observed in sulfate anolyte. These products have not been reported previously for hydroxyl radical-mediated oxidation of ICM. Given that electron-transfer mechanism is more typical for sulfate than for hydroxyl radicals, formation of hydroxylamine and nitro-derivatives of ICM was assigned to one

Full Text Available Abstract A conductive boron-dopeddiamond (BDD grown on a fused silica/quartz has been investigated. Diamond thin films were deposited by the microwave plasma enhanced chemical vapor deposition (MW PECVD. The main parameters of the BDD synthesis, i.e. the methane admixture and the substrate temperature were investigated in detail. Preliminary studies of optical properties were performed to qualify an optimal CVD synthesis and film parameters for optical sensing applications. The SEM micro-images showed the homogenous, continuous and polycrystalline surface morphology; the mean grain size was within the range of 100-250 nm. The fabricated conductive boron-dopeddiamond thin films displayed the resistivity below 500 mOhm cm-1 and the transmittance over 50% in the VIS-NIR wavelength range. The studies of optical constants were performed using the spectroscopic ellipsometry for the wavelength range between 260 and 820 nm. A detailed error analysis of the ellipsometric system and optical modelling estimation has been provided. The refractive index values at the 550 nm wavelength were high and varied between 2.24 and 2.35 depending on the percentage content of methane and the temperature of deposition.

Hot-filament chemical vapor deposition (HFCVD) was used to prepare boron-doped nanocrystalline diamond (BDND) nanoflowers on a Cu substrate with a Cu(OH){sub 2} dendritic architecture that had been formed by using electrostatic self-assembly (ESA) method with nanodiamond particles. The formation of diamond nanoflowers is controlled by the reaction time between the Cu(OH){sub 2} nanoflowers and the polymeric linker for the electrostatic attachment of nanodiamonds and by the deposition time for CVD diamond growth with a high nucleation density. Through analysis by field emission scanning electron microscopy (FESEM) and Raman spectroscopy, the optimal conditions for the synthesis of BDND nanoflowers are determined, and a possible explanation is provided.

Hot-filament chemical vapor deposition (HFCVD) was used to prepare boron-doped nanocrystalline diamond (BDND) nanoflowers on a Cu substrate with a Cu(OH) 2 dendritic architecture that had been formed by using electrostatic self-assembly (ESA) method with nanodiamond particles. The formation of diamond nanoflowers is controlled by the reaction time between the Cu(OH) 2 nanoflowers and the polymeric linker for the electrostatic attachment of nanodiamonds and by the deposition time for CVD diamond growth with a high nucleation density. Through analysis by field emission scanning electron microscopy (FESEM) and Raman spectroscopy, the optimal conditions for the synthesis of BDND nanoflowers are determined, and a possible explanation is provided.

Highlights: • 100% of COD and ∼70% of DOC was removed in both cell configurations. • ∼21.7 mg L{sup −1} of AOCl and ∼2.3 mg L{sup −1} of AOBr was formed regardless of the membrane use. • The TEQ was far lower than expected given the high AOCl concentrations. • The undivided cell consumed lower energy compared to the divided cell. - Abstract: An undivided electrolytic cell may offer lower electrochlorination through reduction of chlorine/hypochlorite at the cathode. This study investigated the performance of electrooxidation of reverse osmosis concentrate using boron-dopeddiamondelectrodes in membrane-divided and undivided cells. In both cell configurations, similar extents of chemical oxygen demand and dissolved organic carbon removal were obtained. Continuous formation of chlorinated organic compounds was observed regardless of the membrane presence. However, halogenation of the organic matter did not result in a corresponding increase in toxicity (Vibrio fischeri bioassay performed on extracted samples), with toxicity decreasing slightly until 10 Ah L{sup −1}, and generally remaining near the initial baseline-toxicity equivalent concentration (TEQ) of the raw concentrate (i.e., ∼2 mg L{sup −1}). The exception was a high range toxicity measure in the undivided cell (i.e., TEQ = 11 mg L{sup −1} at 2.4 Ah L{sup −1}), which rapidly decreased to 4 mg L{sup −1}. The discrepancy between the halogenated organic matter and toxicity patterns may be a consequence of volatile and/or polar halogenated by-products formed in oxidation by OH· electrogenerated at the anode. The undivided cell exhibited lower energy compared to the divided cell, 0.25 kWh gCOD{sup −1} and 0.34 kWh gCOD{sup −1}, respectively, yet it did not demonstrate any improvement regarding by-products formation.

A temperature of 3500 degrees C was generated using a diamond resistance heater in a large-volume Kawai-type high-pressure apparatus. Re and LaCrO(3) have conventionally been used for heaters in high-pressure studies but they cannot generate temperatures higher than 2900 degrees C and make in situ x-ray observations difficult due to their high x-ray absorption. Using a boron-dopeddiamond heater overcomes these problems and achieves stable temperature generation for pressure over 10 GPa. The heater starting material is a cold-compressed mixture of graphite with boron used to avoid the manufacturing difficulties due to the extreme hardness of diamond. The diamond heater was synthesized in situ from the boron-graphite mixture at temperature of 1600+/-100 degrees C and pressure of 20 GPa. By using the proposed technique, we have employed the diamond heater for high-temperature generation in a large-volume high-pressure apparatus. Achievement of temperatures above 3000 degrees C allows us to measure the melting points of the important constituents in earth's mantle (MgSiO(3), SiO(2), and Al(2)O(3)) and core (Fe and Ni) at extremely high pressures.

Borondopeddiamond (BDD) was synthesized under high pressure and high temperature (HPHT) of 7 GPa, 1230 °C in a short time of 10 s from a powder mixtures of detonation nanodiamond (DND), pentaerythritol C5H8(OH)4 and amorphous boron. SEM, TEM, XRD, XPS, FTIR and Raman spectroscopy indicated that BDD nano- and micro-crystals have formed by consolidation of DND particles (4 nm in size). XRD showed the enlargement of crystallites size to 6-80 nm and the increase in diamond lattice parameter by 0.02-0.07% without appearance of any microstrains. Raman spectroscopy was used to estimate the content of boron atoms embedded in the diamond lattice. It was found that the Raman diamond peak shifts significantly from 1332 cm-1 to 1290 cm-1 without appearance of any non-diamond carbon. The correlation between Raman peak position, its width, and boron content in diamond is proposed. Hydrogenated diamond carbon in significant amount was detected by IR spectroscopy and XPS. Due to the doping with boron content of about 0.1 at%, the electrical conductivity of the diamond achieved approximately 0.2 Ω-1 cm-1. Reaction mechanism of diamond growth (models of recrystallization and oriented attachment) is discussed, including the initial stages of pentaerythritol pyrolysis and thermal desorption of functional groups from the surface of DND particles with the generation of supercritical fluid of low-molecular substances (H2O, CH4, CO, CO2, etc.), as well as byproducts formation (B2O3, B4C).

Electrochemical oxidation of biologically-pretreated dye wastewater was performed in a boron-dopeddiamond (BDD) anode system. After electrolysis of 12 h, the COD was decreased from 532 to 99 mg L -1 ( -1 , the National Discharge Standard of China). More importantly, the destination of organic pollutants during electrochemical oxidation process was carefully investigated by molecular weight distribution measurement, resin fractionation, ultraviolet-visible spectroscopy, HPLC and GC-MS analysis, and toxicity test. As results, most organic pollutants were completely removed by electrochemical oxidation and the rest was primarily degraded to simpler compounds (e.g., carboxylic acids and short-chain alkanes) with less toxicity, which demonstrated that electrochemical oxidation of biologically-pretreated dye wastewater with BDD anode was very effective and safe. Especially, the performance of BDD anode system in degradation of large molecular organics such as humic substances makes it very promising in practical applications as an advanced treatment of biologically-pretreated wastewaters.

Full Text Available Gold nanoparticles were prepared by electrochemical deposition on highly oriented pyrolytic graphite (HOPG and boron-doped, epitaxial 100-oriented diamond layers. Using a potentiostatic double pulse technique, the average particle size was varied in the range from 5 nm to 30 nm in the case of HOPG as a support and between < 1 nm and 15 nm on diamond surfaces, while keeping the particle density constant. The distribution of particle sizes was very narrow, with standard deviations of around 20% on HOPG and around 30% on diamond. The electrocatalytic activity towards hydrogen evolution and oxygen reduction of these carbon supported gold nanoparticles in dependence of the particle sizes was investigated using cyclic voltammetry. For oxygen reduction the current density normalized to the gold surface (specific current density increased for decreasing particle size. In contrast, the specific current density of hydrogen evolution showed no dependence on particle size. For both reactions, no effect of the different carbon supports on electrocatalytic activity was observed.

Full Text Available Continuing previous investigations, direct surface modifications of boron-dopeddiamond (BDD electrodes with metal oxides (PtOx, RuO2, IrO2 and PbO2 and with some mixed composites were carried out by the Sol-Gel technique. The materials were studied by atomic force microscopy (AFM to determine their surface topologies and by electrochemical techniques to establish the catalytic activity towards the oxygen evolution reaction (OER and also, for the PtOx and PtOx-RuO2 composites, the ethanol oxidation reactions in acid media. The stability of PtOx coating covered by a Nafion® film was also tested by long-term operation. The AFM results indicated sites of heterogeneous deposition and the electrochemical studies demonstrated that the active surface area changed considerably with the proposed method of modification. The IrO2/BDD electrode showed the best performance to the OER with the onset of the oxidation current at ~1.4 V, a value 200 mV lower than for the PtOx/BDD electrode. The enhanced stability of PtOx/BDD electrodes achieved by the application of a Nafion® film and already reported in acid media was further proved using the ethanol oxidation reaction. Only a small loss of activity (6% was observed after 4-hours electrolysis while one-thousand voltammetric cycles left the surface practically unchanged. In addition, preliminary studies for the same reaction on PtOx/BDD and PtOx-RuO2/BDD electrodes demonstrated the excellent activity of these mixed Sol-Gel coatings on the BDD surface and the possibility of further investigations for practical applications.

This study aims the removal of a carbamate herbicide, propham, from aqueous solution by direct electrochemical advanced oxidation process using a boron-dopeddiamond (BDD) anode. This electrode produces large quantities of hydroxyl radicals from oxidation of water, which leads to the oxidative degradation of propham up to its total mineralization. Effect of operational parameters such as current, temperature, pH and supporting electrolyte on the degradation and mineralization rate was studied. The applied current and temperature exert a prominent effect on the total organic carbon (TOC) removal rate of the solutions. The mineralization of propham can be performed at any pH value between 3 and 11 without any loss in oxidation efficiency. The propham decay and its overall mineralization reaction follows a pseudo-first-order kinetics. The apparent rate constant value of propham oxidation was determined as 4.8 x 10(-4)s(-1) at 100 mA and 35 degrees C in the presence of 50mM Na(2)SO(4) in acidic media (pH: 3). A general mineralization sequence was proposed considering the identified oxidation intermediates.

Boron-dopeddiamond (BDD) electrodes are promising anode materials in electrochemical treatment of wastewaters containing bio-refractory organic compounds due to their strong oxidation capability and remarkable corrosion stability. In order to further improve the performance of BDD anode system, electrochemical degradation of p-nitrophenol were initially investigated at the BDD anode in the presence of zero-valent iron (ZVI). The results showed that under acidic condition, the performance of BDD anode system containing zero-valent iron (BDD-ZVI system) could be improved with the joint actions of electrochemical oxidation at the BDD anode (39.1%), Fenton's reaction (28.5%), oxidation–reduction at zero-valent iron (17.8%) and coagulation of iron hydroxides (14.6%). Moreover, it was found that under alkaline condition the performance of BDD-ZVI system was significantly enhanced, mainly due to the accelerated release of Fe(II) ions from ZVI and the enhanced oxidation of Fe(II) ions. The dissolved oxygen concentration was significantly reduced by reduction at the cathode, and consequently zero-valent iron corroded to Fe(II) ions in anaerobic highly alkaline environments. Furthermore, the oxidation of released Fe(II) ions to Fe(III) ions and high-valent iron species (e.g., FeO 2+ , FeO 4 2− ) was enhanced by direct electrochemical oxidation at BDD anode.

The electrochemical properties of doped diamondelectrodes (10 17 -10 19 B cm -3 ) grown on carbon fiber cloths in H 2 SO 4 0.1 mol L -1 electrolyte were investigated. Cyclic voltammograms of B-doped diamond/carbon fiber cloth and carbon fiber cloth electrodes showed that both kinds of electrodes possess similar working potential windows of about 2.0 V. The electrode capacitance was determined by impedance spectroscopy and chronopotentiometry measurements and very close values were obtained. The capacitance values of the diamond film on carbon fiber cloths were 180 times higher than the ones of diamond films on Si. In this paper we have also discussed the capacitance frequency dependence of diamond/carbon cloth electrodes

Natural diamond is an exceptional prospect for clinical radiation dosimetry due to its tissue-equivalence properties and being chemically inert. The use of diamond in radiation dosimetry has been halted by the high market price; although recently the capability of growing high quality CVD diamond has renewed the interest in using diamond films as radiation dosimeters. In the present work we have characterized the dosimetric properties of diamond films synthesized by the HFCVD method. The thermoluminescence and the optically stimulated luminescence of beta exposed diamond sample containing a B/C 4000 ppm doping presents excellent properties suitable for dosimetric applications with β-ray doses up to 3.0 kGy. The observed OSL and TL performance is reasonable appropriate to justify further investigation of diamond films as dosimeters for ionizing radiation, specially in the radiotherapy field where very well localized and in vivo and real time radiation dose applications are essential.

The secondary electron emission from a 2 μm thick boron-dopeddiamond film under ion (4.6 endash 7.7 MeV He + )impact is reported. The yield under ions impact is found to be remarkably high, stable over a period of many months, and independent of which side of the film (i.e., growth or substrate side) is exposed to the ion flux. By taking advantage of the high secondary-electron yield, the passage of each ion through the film could be detected with an efficiency of close to 100%, which to the best of our knowledge is the highest efficiency recorded to date for any thin-film window. This finding has an immediate application in single-ion irradiation systems where a thin vacuum window is required to allow extraction of an ion beam from the vacuum into air and at the same time offer 100% efficiency for the detection of the passage of the ion through the window. copyright 1997 American Institute of Physics

Carbon nanomaterials such as nanotubes, nanoflakes/nanowalls, and graphene have been used as electron sources due to their superior field electron emission (FEE) characteristics. However, these materials show poor stability and short lifetimes, which prevent their use in practical device applications. The aim of this study was to find an innovative nanomaterial possessing both high robustness and reliable FEE behavior. Herein, a hybrid structure of self-organized multi-layered graphene (MLG)-borondopeddiamond (BDD) nanowall materials with superior FEE characteristics was successfully synthesized using a microwave plasma enhanced chemical vapor deposition process. Transmission electron microscopy reveals that the as-prepared carbon clusters have a uniform, dense, and sharp nanowall morphology with sp 3 diamond cores encased by an sp 2 MLG shell. Detailed nanoscale investigations conducted using peak force-controlled tunneling atomic force microscopy show that each of the core-shell structured carbon cluster fields emits electrons equally well. The MLG-BDD nanowall materials show a low turn-on field of 2.4 V μm -1 , a high emission current density of 4.2 mA cm -2 at an applied field of 4.0 V μm -1 , a large field enhancement factor of 4500, and prominently high lifetime stability (lasting for 700 min), which demonstrate the superiority of these materials over other hybrid nanostructured materials. The potential of these MLG-BDD hybrid nanowall materials in practical device applications was further illustrated by the plasma illumination behavior of a microplasma device with these materials as the cathode, where a low threshold voltage of 330 V (low threshold field of 330 V mm -1 ) and long plasma stability of 358 min were demonstrated. The fabrication of these hybrid nanowalls is straight forward and thereby opens up a pathway for the advancement of next-generation cathode materials for high brightness electron emission and microplasma-based display devices.

Graphical abstract: - Highlights: • Mineralization of secondary effluent by anodic oxidation with BDD anode. • Complete removal of 29 pharmaceuticals and pesticides at trace level concentrations. • Organochlorine and organobromine byproducts were formed at low μM concentrations. • Chlorine species evolution assessed to evaluate the anodic oxidation applicability. - Abstract: Electrochemical advanced oxidation processes (EAOPs) have been widely investigated as promising technologies to remove trace organic contaminants from water, but have rarely been used for the treatment of real waste streams. Anodic oxidation with a boron-dopeddiamond (BDD) anode was applied for the treatment of secondary effluent from a municipal sewage treatment plant containing 29 target pharmaceuticals and pesticides. The effectiveness of the treatment was assessed from the contaminants decay, dissolved organic carbon and chemical oxygen demand removal. The effect of applied current and pH was evaluated. Almost complete mineralization of effluent organic matter and trace contaminants can be obtained by this EAOP primarily due to the action of hydroxyl radicals formed at the BDD surface. The oxidation of Cl{sup −} ions present in the wastewater at the BDD anode gave rise to active chlorine species (Cl{sub 2}/HClO/ClO{sup −}), which are competitive oxidizing agents yielding chloramines and organohalogen byproducts, quantified as adsorbable organic halogen. However, further anodic oxidation of HClO/ClO{sup −} species led to the production of ClO{sub 3}{sup −} and ClO{sub 4}{sup −} ions. The formation of these species hampers the application as a single-stage tertiary treatment, but posterior cathodic reduction of chlorate and perchlorate species may reduce the risks associated to their presence in the environment.

Molybdenum-rhenium (Mo/Re) and tungsten-rhenium (W/Re) alloys were investigated as substrates for thin-film, polycrystalline boron-dopeddiamondelectrodes. Traditional, carbide-forming metal substrates adhere strongly to diamond but lose their ductility during exposure to the high-temperature (1000°C) diamond, chemical vapor deposition environment. Boron-doped semi-metallic diamond was selectively deposited for up to 20 hours on one end of Mo/Re (47.5/52.5 wt.%) and W/Re (75/25 wt.%) alloy wires. Conformal diamond films on the alloys displayed grain sizes and Raman signatures similar to films grown on tungsten; in all cases, the morphology and Raman spectra were consistent with well-faceted, microcrystalline diamond with minimal sp 2 carbon content. Cyclic voltammograms of dopamine in phosphate-buffered saline (PBS) showed the wide window and low baseline current of high-quality diamondelectrodes. In addition, the films showed consistently well-defined, dopamine electrochemical redox activity. The Mo/Re substrate regions that were uncoated but still exposed to the diamond-growth environment remained substantially more flexible than tungsten in a bend-to-fracture rotation test, bending to the test maximum of 90° and not fracturing. The W/Re substrates fractured after a 27° bend, and the tungsten fractured after a 21° bend. Brittle, transgranular cleavage fracture surfaces were observed for tungsten and W/Re. A tension-induced fracture of the Mo/Re after the prior bend test showed a dimple fracture with a visible ductile core. Overall, the Mo/Re and W/Re alloys were suitable substrates for diamond growth. The Mo/Re alloy remained significantly more ductile than traditional tungsten substrates after diamond growth, and thus may be an attractive metal substrate for more ductile, thin-film diamondelectrodes.

In this research work, a photoassisted electrochemical system under recirculation mode and with UV irradiation was designed for treatment of C.I. Acid Blue 92 (AB92) as a model anionic azo dye in aqueous solution. Degradation experiments were carried out with boron-dopeddiamond (BDD) anode and carbon nanotubes-polytetrafluoroethylene (CNTs-PTFE) cathode in the presence of sulfate as an electrolyte. A comparative study of AB92 degradation by photolysis, electrochemical oxidation and photoassisted electrochemical processes after 45 min of treatment demonstrated that degradation efficiency was 27.89, 37.65 and 95.86%, respectively. Experimental data revealed that the degradation rate of AB92 in all of the processes obeyed pseudo-first-order kinetics and application of photoassisted electrochemical system reduced electrical energy per order (E EO ), considerably. Degradation efficiency of photoassisted electrochemical process enhanced by increasing applied current and flow rate values, but vice versa trend was observed for initial dye concentration and an optimum amount of 6 was obtained for initial pH. The TOC measurement results demonstrated that 93.24% of organic substrates were mineralized after 120 min of photoassisted electrochemical process and GC–Mass analysis was performed for identification of degradation intermediates

Electrochemical oxidation of resorcinol in aqueous medium using boron-dopeddiamond anode (BDD) was investigated in a batch electrochemical reactor in the presence of Na 2 SO 4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100-500 g/L), current density (2-10 mA/cm 2 ), Na 2 SO 4 concentration (0-20 g/L), and reaction temperature (25-45°C) was analyzed on electrochemical oxidation using response surface methodology (RSM). The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm 2 current density, 12 g/L Na 2 SO 4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction.

Full Text Available Electrochemical oxidation of resorcinol in aqueous medium using boron-dopeddiamond anode (BDD was investigated in a batch electrochemical reactor in the presence of Na2SO4 supporting electrolyte. The effect of process parameters such as resorcinol concentration (100–500 g/L, current density (2–10 mA/cm2, Na2SO4 concentration (0–20 g/L, and reaction temperature (25–45°C was analyzed on electrochemical oxidation using response surface methodology (RSM. The optimum operating conditions were determined as 300 mg/L resorcinol concentration, 8 mA/cm2 current density, 12 g/L Na2SO4 concentration, and 34°C reaction temperature. One hundred percent of resorcinol removal and 89% COD removal were obtained in 120 min reaction time at response surface optimized conditions. These results confirmed that the electrochemical mineralization of resorcinol was successfully accomplished using BDD anode depending on the process conditions, however the formation of intermediates and by-products were further oxidized at much lower rate. The reaction kinetics were evaluated at optimum conditions and the reaction order of electrochemical oxidation of resorcinol in aqueous medium using BDD anode was determined as 1 based on COD concentration with the activation energy of 5.32 kJ/mol that was supported a diffusion-controlled reaction.

On the other hand, nanocrystalline diamond (NCD) or ultra-NCD film has low surface roughness and fine nano-scaled grains. Therefore, a multilayer-diamond coating system was designed to improve the mechanical and tribological properties by combining the advantages of boron-dopeddiamond (BDD), MCD and. NCD.

We have developed a new fabrication process to decrease the effective activation energy of B atoms doped in diamond without a significant decrease in the carrier mobility by fabricating heavily B-doped clusters with very low mobility which are embedded in lightly-B-doped diamond layers. The resistivities of the heavily B-doped and unintentionally B-doped diamond stacked layers had almost no temperature dependence, suggesting the presence of an impurity-band conduction in these diamond layers. On the other hand, the resistivities of the samples after the embedding growth process of the stacked layers that had been appropriately divided to innumerable small clusters by means of a suitable etching process increased with decreasing the temperature from 330 to 130 K. The effective activation energies and Hall mobilities at room temperature of both samples were estimated to be 0.21 eV, 106 cm2 V-1 s-1 for micron-sized clusters and 0.23 eV, 470 cm2 V-1 s-1 for nano-sized clusters, respectively, indicating that the diamond film structure fabricated in this work is effective for the improvement of the p-type performance for the B-doped CVD diamond.

B-doped diamond has become the ultimate material for applications in the field of microelectromechanical systems (MEMS), which require both highly wear resistant and electrically conductive diamond films and microstructures. Despite the extensive research of the tribological properties of undoped

Chemical vapor deposition (CVD) diamond coated cutting tool has excellent cutting performance, it is the most ideal tool for the processing of nonferrous metals and alloys, composites, nonmetallic materials and other difficult-to-machine materials efficiently and accurately. Depositing CVD diamond coating on the cemented carbide with high cobalt content can improve its toughness and strength, therefore, it is very important to research on the preparation technology and cu...

Amaranth dye is used widely in the processing of paper, textiles, foods, cosmetics, beverages and medicines, and effluents contaminated with this compound are discharged daily into the environment. Recent studies have shown that azo dyes, especially those such as amaranth dye that have been classified as endocrine disruptors, may cause adverse effects to animal and human health. This paper describes the application of electrochemical oxidation (with a boron-dopeddiamond BDD thin-film anode) coupled with ultrasound sonolysis (20 kHz and 523 W cm −2 ) to the removal of amaranth dye from dilute alkaline solution. The electrochemical and sonoelectrochemical processes (ECh and SECh, respectively) were carried out at constant current density (10 to 50 mA cm −2 ) in a single compartment cylindrical cell. Sonolysis was virtually less useful for the decolorization and degradation of amaranth dye, whilst ECh and SECh were more effective in degrading the dye with almost complete removal (90 - 95%) attained after 90 min of experiment at an applied current density of 50 mA cm −2 . Degradation of the dye followed pseudo first-order kinetics in both processes, but the rate of reaction was faster with the SECh treatment confirming a synergistic effect between the cavitation process and the electrochemical system. Additionally, at low applied current densities (10 and 25 mA cm −2 ), SECh was considerably more effective than ECh for the amaranth dye mineralization. Although at 35 and 50 mA cm −2 , the two processes showed the respective removal of total organic carbon values: (i) 85% for the ECh and 90% for the SECh at 35 mA cm −2 ; (ii) 96% for the ECh and 98% for the SECh at 50 mA cm −2 . It is concluded that SECh presented the most favorable results for the decontamination of wastewaters containing azo dye compounds

Graphical abstract: - Highlights: • Combining electrolysis with ozonation greatly enhances nitrophenol mineralization. • O{sub 3} can rapidly degrade nitrophenol to carboxylic acids in the bulk solution. • Carboxylic acids can be mineralized by ·OH generated from multiple sources in the electrolysis-O{sub 3} process. • Electrolysis and ozonation can compensate for each other's weakness on pollutant degradation. - Abstract: Electrolysis and ozonation are two commonly used technologies for treating wastewaters contaminated with nitrophenol pollutants. However, they are often handicapped by their slow kinetics and low yields of total organic carbon (TOC) mineralization. To improve TOC mineralization efficiency, we combined electrolysis using a boron-dopeddiamond (BDD) anode with ozonation (electrolysis-O{sub 3}) to treat a p-nitrophenol (PNP) aqueous solution. Up to 91% TOC was removed after 60 min of the electrolysis-O{sub 3} process. In comparison, only 20 and 44% TOC was respectively removed by individual electrolysis and ozonation treatment conducted under similar reaction conditions. The result indicates that when electrolysis and ozonation are applied simultaneously, they have a significant synergy for PNP mineralization. This synergy can be mainly attributed to (i) the rapid degradation of PNP to carboxylic acids (e.g., oxalic acid and acetic acid) by O{sub 3}, which would otherwise take a much longer time by electrolysis alone, and (ii) the effective mineralization of the ozone-refractory carboxylic acids to CO{sub 2} by ·OH generated from multiple sources in the electrolysis-O{sub 3} system. The result suggests that combining electrolysis with ozonation can provide a simple and effective way to mutually compensate the limitations of the two processes for degradation of phenolic pollutants.

The electrochemical oxidation of phenolic compounds in aqueous media is known to be affected by the formation of electro-polymerized organic layers which lead to partial or complete electrode blocking. In this study the effect of high intensity microwave radiation applied locally at the electrode surface is investigated for the oxidation of phenol and triclosan in alkaline solution at a 500 μm diameter glassy carbon or at a 500 μm x 500 μm boron-dopeddiamondelectrode. The temperature at the electrode surface and mass transport enhancement are determined by calibration with the Fe(CN) 6 3-/4- redox system in aqueous 0.3 M NaOH and 0.2 NaCl (pH 12) solution. The calibration shows that strong thermal and mass transport effects occur at both glassy carbon and boron-dopeddiamondelectrodes. The average electrode temperature reaches up to 390 K and mass transport enhancements of more than 20-fold are possible. For the phenol electro-oxidation at glassy carbon electrodes and at a concentration below 2 mM a multi-electron oxidation (ca. 4 electrons) occurs in the presence of microwave radiation. For the electro-oxidation of the more hydrophobic triclosan only the one-electron oxidation occurs. Although currents are enhanced in presence of microwave radiation, rapid blocking of the electrode surface in particular at high phenol concentrations still occurs

The electrochemical oxidation of phenolic compounds in aqueous media is known to be affected by the formation of electro-polymerized organic layers which lead to partial or complete electrode blocking. In this study the effect of high intensity microwave radiation applied locally at the electrode surface is investigated for the oxidation of phenol and triclosan in alkaline solution at a 500 {mu}m diameter glassy carbon or at a 500 {mu}m x 500 {mu}m boron-dopeddiamondelectrode. The temperature at the electrode surface and mass transport enhancement are determined by calibration with the Fe(CN){sub 6}{sup 3-/4-} redox system in aqueous 0.3 M NaOH and 0.2 NaCl (pH 12) solution. The calibration shows that strong thermal and mass transport effects occur at both glassy carbon and boron-dopeddiamondelectrodes. The average electrode temperature reaches up to 390 K and mass transport enhancements of more than 20-fold are possible. For the phenol electro-oxidation at glassy carbon electrodes and at a concentration below 2 mM a multi-electron oxidation (ca. 4 electrons) occurs in the presence of microwave radiation. For the electro-oxidation of the more hydrophobic triclosan only the one-electron oxidation occurs. Although currents are enhanced in presence of microwave radiation, rapid blocking of the electrode surface in particular at high phenol concentrations still occurs. (author)

Specific electrochemical cleavage of peptide bonds at the C-terminal side of tyrosine and tryptophan generates peptides amenable to liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis for protein identification. To this end we developed a microfluidic electrochemical cell of 160 nL

Specific electrochemical cleavage of peptide bonds at the C-terminal side of tyrosine and tryptophan generates peptides amenable to liquid chromatography-tandem mass spectrometry (LC-MS/MS) analysis for protein identification. To this end we developed a microfluidic electrochemical cell of 160 nL

Titanium alloy (Ti6Al4V) substrates were deposited with smooth multilayer coatings, by hot filament chemical vapour deposition technique. The effect of borondoping on lattice parameter, residual stresses, hardness and coefficient of friction in multilayer-diamond coating system was studied. The frictional behaviour of the ...

Highlights: • Degradation of Reactive Blue 15 solution at pH 3.0 by electrochemical oxidation, electro-Fenton and photoelectro-Fenton. • Hard destruction of the dye and its products by BDD(·OH) and much more rapidly by ·OH. • 94% mineralization by the most powerful photoelectro-Fenton at 66.7 mA cm −2 , with acetic acid accumulation. • 25 aromatics and heteroaromatics, 30 hydroxylated derivatives and 4 carboxylic acids as products. • Release of Cl − , SO 4 2− and pre-eminently NO 3 − during dye mineralization. - Abstract: The degradation of the copper-phthalocyanine dye Reactive Blue 15 dye in sulfate medium has been comparatively studied by electrochemical oxidation with electrogenerated H 2 O 2 (EO-H 2 O 2 ), electro-Fenton (EF) and photoelectro-Fenton (PEF). Experiments with 100 cm 3 solutions of 0.203 mmol dm −3 dye were performed with a stirred tank reactor containing a boron-dopeddiamond (BDD) anode and an air-diffusion cathode for continuous H 2 O 2 production. Experimental conditions of pH 3.0 and 0.50 mmol dm −3 Fe 2+ as catalyst were found optimal for the EF process by the predominant oxidation with hydroxyl radicals formed in the bulk from Fenton’s reaction between added Fe 2+ and generated H 2 O 2 . The kinetics of Reactive Blue 15 abatement was followed by reversed-phase HPLC and always obeyed a pseudo-first-order reaction. The decolorization rate in EO-H 2 O 2 was much lower than dye decay due to the formation of large quantities of colored intermediates under the action of hydroxyl radicals generated at the BDD anode from water oxidation. In contrast, the color and dye removals were much more rapid in EF and PEF by the most efficient oxidation of hydroxyl radicals produced from Fenton’s reaction. PEF was the most powerful treatment owing to the photolytic action of UVA irradiation, yielding 94% mineralization after 360 min at 66.7 mA cm −2 . The effect of current density over the performance of all methods was examined

The discoveries of superconductivity in heavily boron-dopeddiamond (C:B) in 2004 and silicon (Si:B) in 2006 renew the interest in the superconducting state of semiconductors. Charge-carrier doping of wide-gap semiconductors leads to a metallic phase from which upon further doping superconductivity can emerge. Recently, we discovered superconductivity in a closely related system: heavily-borondoped silicon carbide (SiC:B). The sample used for that study consists of cubic and hexagonal SiC ph...

The modification of the diamond surface with organic molecules is a crucial aspect to be considered for any bioapplication of this material. There is great interest in broadening the range of linker molecules that can be covalently bound to the diamond surface. In the case of protein immobilization, the hydropathicity of the surface has a major influence on the protein conformation and, thus, on the functionality of proteins immobilized at surfaces. For electrochemical applications, particular attention has to be devoted to avoid that the charge transfer between the electrode and the redox center embedded in the protein is hindered by a thick insulating linker layer. This paper reports on the grafting of 6-phosphonohexanoic acid on OH-terminated diamond surfaces, serving as linkers to tether electroactive proteins onto diamond surfaces. X-ray photoelectron spectroscopy (XPS) confirms the formation of a stable layer on the surface. The charge transfer between electroactive molecules and the substrate is studied by electrochemical characterization of the redox activity of aminomethylferrocene and cytochrome c covalently bound to the substrate through this linker. Our work demonstrates that OH-terminated diamond functionalized with 6-phosphonohexanoic acid is a suitable platform to interface redox-proteins, which are fundamental building blocks for many bioelectronics applications.

Full Text Available Deep brain stimulation (DBS, a surgical technique to treat certain neurologic and psychiatric conditions, relies on pre-determined stimulation parameters in an open-loop configuration. The major advancement in DBS devices is a closed-loop system that uses neurophysiologic feedback to dynamically adjust stimulation frequency and amplitude. Stimulation-driven neurochemical release can be measured by fast-scan cyclic voltammetry (FSCV, but existing FSCV electrodes rely on carbon fiber, which degrades quickly during use and is therefore unsuitable for chronic neurochemical recording. To address this issue, we developed durable, synthetic boron-dopeddiamond-based electrodes capable of measuring neurochemical release in humans. Compared to carbon fiber electrodes, they were more than two orders-of-magnitude more physically-robust and demonstrated longevity in vitro without deterioration. Applied for the first time in humans, diamondelectrode recordings from thalamic targets in patients (n=4 undergoing DBS for tremor produced signals consistent with adenosine release at a sensitivity comparable to carbon fiber electrodes.

Neural interfacing still requires highly stable and biocompatible materials, in particular for in vivo applications. Indeed, most of the currently used materials are degraded and/or encapsulated by the proximal tissue leading to a loss of efficiency. Here, we considered borondopeddiamond microelectrodes to address this issue and we evaluated the performances of a diamond microelectrode array. We described the microfabrication process of the device and discuss its functionalities. We characterized its electrochemical performances by cyclic voltammetry and impedance spectroscopy in saline buffer and observed the typical diamondelectrode electrochemical properties, wide potential window and low background current, allowing efficient electrochemical detection. The charge storage capacitance and the modulus of the electrochemical impedance were found to remain in the same range as platinum electrodes used for standard commercial devices. Finally we observed a reduced Magnetic Resonance Imaging artifact when the device was implanted on a rat cortex, suggesting that borondoped-diamond is a very promising electrode material allowing functional imaging. - Highlights: • Microfabrication of all-diamond microelectrode array • Evaluation of as-grown nanocrystalline boron-dopeddiamond for electrical neural interfacing • MRI compatibility of nanocrystalline boron-dopeddiamond.

Full Text Available Nowadays, synthetic diamond has been studied for its application in wastewater treatment, electroanalysis, organic synthesis and sensor areas; however, its use in the water disinfection/purification is its most relevant application. The new electrochemistry applications of diamondelectrodes open new perspectives for an easy, effective, and chemical free water treatment. This article highlights and summarizes the results of a selection of papers dealing with electrochemical disinfection using synthetic diamond films.

X-ray absorption (XAS) and emission (XES) spectroscopy near B K and C K edges have been performed on metallic ( ˜0.1at.% B, B-diamond) and semiconducting ( ˜0.03at.% B and N, BN-diamond) doped diamond films. Both B K XAS and XES spectra show a metallic partial density of states (PDOS) with the Fermi energy of 185.3eV , and there is no apparent boron-concentration dependence in contrast to the different electric property. In C K XAS spectrum of B-diamond, the impurity state ascribed to boron is clearly observed near the Fermi level. The Fermi energy is found to be almost same with the top of the valence band of nondoped diamond: EV=283.9eV . C K XAS of BN-diamond shows both the B-induced shallow level and N-induced deep and broad levels as the in-gap states, in which the shallow level is in good agreement with the activation energy (Ea=0.37eV) estimated from the temperature dependence of the conductivity; namely, the change in C2p PDOS of impurity-induced metallization is directly observed. The electric property of this diamond is ascribed mainly to the electronic structure of C2p near the Fermi level. The observed XES spectra are compared with the discrete variational Xα ( DVXα ) cluster calculation. The DVXα result supports the strong hybridization between B2p and C2p observed in XAS and XES spectra, and suggests that the small amount of boron (⩽0.1at.%) in diamond occupies the substitutional site rather than interstitial site.

Full Text Available The discoveries of superconductivity in heavily boron-dopeddiamond in 2004 and silicon in 2006 have renewed the interest in the superconducting state of semiconductors. Charge-carrier doping of wide-gap semiconductors leads to a metallic phase from which upon further doping superconductivity can emerge. Recently, we discovered superconductivity in a closely related system: heavily boron-doped silicon carbide. The sample used for that study consisted of cubic and hexagonal SiC phase fractions and hence this led to the question which of them participated in the superconductivity. Here we studied a hexagonal SiC sample, free from cubic SiC phase by means of x-ray diffraction, resistivity, and ac susceptibility.

The discoveries of superconductivity in heavily boron-dopeddiamond in 2004 and silicon in 2006 have renewed the interest in the superconducting state of semiconductors. Charge-carrier doping of wide-gap semiconductors leads to a metallic phase from which upon further doping superconductivity can emerge. Recently, we discovered superconductivity in a closely related system: heavily boron-doped silicon carbide. The sample used for that study consisted of cubic and hexagonal SiC phase fractions and hence this led to the question which of them participated in the superconductivity. Here we studied a hexagonal SiC sample, free from cubic SiC phase by means of x-ray diffraction, resistivity, and ac susceptibility.

The degradation of a 41 mg dm -3 ibuprofen (2-(4-isobutylphenyl)propionic acid) solution of pH 3.0 has been comparatively studied by electrochemical advanced oxidation processes (EAOPs) like electro-Fenton, UVA photoelectro-Fenton and solar photoelectro-Fenton at constant current density. Experiments were performed in a one-compartment cell with a Pt or boron-dopeddiamond (BDD) anode and an O 2 -diffusion cathode. Heterogeneous hydroxyl radical (·OH) is generated at the anode surface from water oxidation, while homogeneous ·OH is formed from Fenton's reaction between Fe 2+ and H 2 O 2 generated at the cathode, being its production strongly enhanced from photo-Fenton reaction induced by sunlight. Higher mineralization is attained in all methods using BDD instead Pt, because the former produces greater quantity of ·OH enhancing the oxidation of pollutants. The mineralization rate increases under UVA and solar irradiation by the rapid photodecomposition of complexes of Fe(III) with acidic intermediates. The most potent method is solar photoelectro-Fenton with BDD giving 92% mineralization due to the formation of a small proportion of highly persistent final by-products. The effect of Fe 2+ content, pH and current density on photoelectro-Fenton degradation has been studied. The ibuprofen decay always follows a pseudo-first-order kinetics and its destruction rate is limited by current density and UV intensity. Aromatics such as 1-(1-hydroxyethyl)-4-isobutylbenzene, 4-isobutylacetophenone, 4-isobutylphenol and 4-ethylbenzaldehyde, and carboxylic acids such as pyruvic, acetic, formic and oxalic have been identified as oxidation by-products. Oxalic acid is the ultimate by-product and the fast photodecarboxylation of its complexes with Fe(III) under UVA or solar irradiation explains the higher oxidation power of photoelectro-Fenton methods in comparison to electro-Fenton procedures

Full Text Available Chemical doping is an effective approach to improve the property of carbon material. In this study borondoped graphene with 3D structure used as the electrode was investigated. Borondoped graphene was prepared through freeze-dried process followed by pyrolysis of graphene oxide (GO with three types of chemical substances; boron oxide, boric acid, and boron powder in an argon and hydrogen atmosphere at 1000 C for 3 hours. The difference of chemical composition generated a different percentage of boron bond with GO. The results shows that the highest electrochemical performance was found in graphene samples with the addition of boric acid (BA 86 F/g, followed by boron oxide (BO 59.2 F/g, and boron powder (BP 2 F/g. It can be caused by boron concentration bound with graphene. The higher concentration of boron could be increased the electrochemical performance due to better of ion movement.

Diamond technology has claimed an important role in industry since non-expensive methods of synthesis such as chemical vapour deposition allow to elaborate cheap polycrystalline diamond. This fact has increased the interest in the scientific community due to the outstanding properties of diamond. Since Pleskov published in 1987 the first paper in electrochemistry, many researchers around the world have studied different aspects of diamond electrochemistry such as reactivity, electrical structure, etc. As part of this worldwide interest these studies reveal new information about diamondelectrodes. These studies report investigation of diamondelectrodes characterized using structural techniques like scanning electrode microscopy and Raman spectroscopy. A new electrochemical theory based on surface states is presented that explains the metal and the semiconductor behaviour in terms of the doping level of the diamondelectrode. In an effort to characterise the properties of diamondelectrodes the band edges for hydrogen and oxygen terminated surface are located in organic solvent, hence avoiding possible interference that are present in aqueous solution. The determination of the band edges is performed by Mott-Schottky studies. These allow the calculation of the flat band potential and therefore the band edges. Additional cyclic voltammetric studies are presented for both types of surface termination. Mott-Schottky data and cyclic voltammograms are compared and explained in terms of the band edge localisation. Non-degenerately p-type semiconductor behaviour is presented for hydrogen terminated borondopeddiamond. Graphitic surface states on oxidised surface borondopeddiamond are responsible for the electrochemistry of redox couples that posses similar energy. Using the simple redox couple 1,4-benzoquinone effect of surface termination on the chemical behaviour of diamond is presented. Hydrogen sublayers in diamondelectrodes seem to play an important role for the

The development of the first all-diamond hydrodynamic flow device for electroanalytical applications is described. Here alternate layers of intrinsic (insulating), conducting (heavily borondoped), and intrinsic polycrystalline diamond are grown to create a sandwich structure. By laser cutting a hole through the material, it is possible to produce a tubular flow ring electrode of a characteristic length defined by the thickness of the conducting layer (for these studies ∼90 μm). The inside of the tube can be polished to 17 ± 10 nm surface roughness using a diamond impregnanted wire resulting in a coplanar, smooth, all-diamond surface. The steady-state limiting current versus volume flow rate characteristics for the one electron oxidation of FcTMA(+) are in agreement with those expected for laminar flow in a tubular electrode geometry. For dopamine detection, it is shown that the combination of the reduced fouling properties of borondopeddiamond, coupled with the flow geometry design where the products of electrolysis are washed away downstream of the electrode, completely eradicates fouling during electrolysis. This paves the way for incorporation of this flow design into online electroanalytical detection systems. Finally, the all diamond tubular flow electrode system described here provides a platform for future developments including the development of ultrathin ring electrodes, multiple apertures for increased current response, and multiple, individually addressable ring electrodes incorporated into the same flow tube.

Diamond in nanoparticle form is a promising material that can be used as a robust and chemically stable catalyst support in fuel cells. It has been studied and characterized physically and electrochemically, in its thin film and powder forms, as reported in the literature. In the present work, the electrochemical properties of undoped and boron-dopeddiamond nanoparticle electrodes, fabricated using the ink-paste method, were investigated. Methanol oxidation experiments were carried out in both half-cell and full fuel cell modes. Platinum and ruthenium nanoparticles were chemically deposited on undoped and borondopeddiamond nanoparticles through the use of NaBH(4) as reducing agent and sodium dodecyl benzene sulfonate (SDBS) as a surfactant. Before and after the reduction process, samples were characterized by electron microscopy and spectroscopic techniques. The ink-paste method was also used to prepare the membrane electrode assembly with Pt and Pt-Ru modified undoped and boron-dopeddiamond nanoparticle catalytic systems, to perform the electrochemical experiments in a direct methanol fuel cell system. The results obtained demonstrate that diamond supported catalyst nanomaterials are promising for methanol fuel cells.

In this work, the effective heating of surrounding water by heavily-boron-doped nanodiamonds (NDs) under laser irradiation of visible wavelength was found. Using Raman scattering spectroscopy of aqueous suspensions of boron-doped NDs, it was found that this abnormally high heating results in the weakening of hydrogen bonds much more so (2-5 times stronger) than for undoped NDs. The property of boron-doped NDs to heat a solvent under the influence of laser radiation (1-5 W cm-2) opens broad prospects for their use to create nanoagents for medical oncology and local hyperthermia.

Unimorph heterostructures based on piezoelectric aluminum nitride (AlN) and diamond thin films are highly desirable for applications in micro- and nanoelectromechanical systems. In this paper, we present a new approach to combine thin conductive boron-doped as well as insulating nanocrystalline diamond (NCD) with sputtered AlN films without the need for any buffer layers between AlN and NCD or polishing steps. The zeta potentials of differently treated nanodiamond (ND) particles in aqueous colloids are adjusted to the zeta potential of AlN in water. Thereby, the nucleation density for the initial growth of diamond on AlN can be varied from very low (10(8) cm(-2)), in the case of hydrogen-treated ND seeding particles, to very high values of 10(11) cm(-2) for oxidized ND particles. Our approach yielding high nucleation densities allows the growth of very thin NCD films on AlN with thicknesses as low as 40 nm for applications such as microelectromechanical beam resonators. Fabricated piezo-actuated micro-resonators exhibit enhanced mechanical properties due to the incorporation of boron-doped NCD films. Highly boron-doped NCD thin films which replace the metal top electrode offer Young's moduli of more than 1000 GPa.

Reactive xenobiotic metabolites and their adduct formation with biomolecules such as proteins are important to study as they can be detrimental to human health. Here, we present a microfluidic electrochemical cell with integrated micromixer to study phase I and phase II metabolism as well as protein

Carbon-based materials show promise, given their light weight, large surface areas and low cost for storage of hydrogen and other gases, e.g., for energy applications. Alas, the interaction of H2 and carbon, 4-5kJ/mol, is insufficient for room-temperature operation. Borondoping of carbon materials could raise the binding energy of H2 to 12-15kJ/mol. The nature of the incorporation of boron into a carbon structure has not been studied so far. In this talk we will address the energetics of boron incorporation into a carbon matrix via adsorption and decomposition of decaborane by first principles calculations. These demonstrate: (a) A strong adsorption of decaborane to carbon (70-80kJ/mol) resulting in easy incorporation of decaborane, sufficient for up to 10-20% B:C at low decaborane vapour pressures. (b) Identification that boron acts as an electron acceptor when incorporated substitutionally into a graphene-like material, as expected due to its valence. (c) The electrostatic field near the molecule is responsible for ca. 2/3 of the enhancement of the H2-adsorbent interaction in aromatic compounds such as pyrene, coronene and ovalene. Supported by DOE DE-FG36-08GO18142, ACS-PRF 52696-ND5, and NSF 1069091.

We have directly measured the solubility of iron in high and low boron-doped silicon using instrumental neutron activation analysis. Iron solubilities were measured at 800, 900, 1000, and 1100thinsp degree C in silicon doped with either 1.5x10 19 or 6.5x10 14 thinspboronthinspatoms/cm 3 . We have measured a greater iron solubility in high boron-doped silicon as compared to low boron-doped silicon, however, the degree of enhancement is lower than anticipated at temperatures >800thinsp degree C. The decreased enhancement is explained by a shift in the iron donor energy level towards the valence band at elevated temperatures. Based on this data, we have calculated the position of the iron donor level in the silicon band gap at elevated temperatures. We incorporate the iron energy level shift in calculations of iron solubility in silicon over a wide range of temperatures and boron-doping levels, providing a means to accurately predict iron segregation between high and low boron-doped silicon. copyright 1998 American Institute of Physics

Diamond is well known to possess many favourable qualities for implantation into living tissue including biocompatibility, biostability, and for some applications hardness. However, conducting diamond has not, to date, been exploited in neural stimulation electrodes due to very low electrochemical double layer capacitance values that have been previously reported. Here we present electrochemical characterization of ultra-nanocrystalline diamondelectrodes grown in the presence of nitrogen (N-UNCD) that exhibit charge injection capacity values as high as 163 µC cm(-2) indicating that N-UNCD is a viable material for microelectrode fabrication. Furthermore, we show that the maximum charge injection of N-UNCD can be increased by tailoring growth conditions and by subsequent electrochemical activation. For applications requiring yet higher charge injection, we show that N-UNCD electrodes can be readily metalized with platinum or iridium, further increasing charge injection capacity. Using such materials an implantable neural stimulation device fabricated from a single piece of bio-permanent material becomes feasible. This has significant advantages in terms of the physical stability and hermeticity of a long-term bionic implant.

Diamond-like carbon (DLC) material is used in blood contacting devices as the surface coating material because of the antithrombogenicity behavior which helps to inhibit platelet adhesion and activation. In this study, DLC films were doped with boron during pulsed plasma chemical vapor deposition (CVD) to improve the blood compatibility. The ratio of boron to carbon (B/C) was varied from 0 to 0.4 in the film by adjusting the flow rate of trimethylboron and acetylene. Tribological tests indicated that borondoping with a low B/C ratio of 0.03 is beneficial for reducing friction (μ = 0.1), lowering hardness and slightly increasing wear rate compared to undoped DLC films. The B/C ratio in the film of 0.03 and 0.4 exhibited highly hydrophilic surface owing to their high wettability and high surface energy. An in vitro platelet adhesion experiment was conducted to compare the blood compatibility of TiNb substrates before and after coating with undoped and borondoped DLC. Films with highly hydrophilic surface enhanced the blood compatibility of TiNb, and the best results were obtained for DLC with the B/C ratio of 0.03. Borondoped DLC films are promising surface coatings for blood contacting devices.

A 10,0 pristine as well as borondoped zigzag single walled carbon nanotube has been analyzed as possible HBr sensor using DFT based ab-initio approach. The variation in band structures, Mulliken charge, NBO charge, binding energy and conductance variation has been analyzed. The CNT observes a lowering of bandgap in presence of HBr molecule near its surface and reduces the metallicity of Borondoped CNT. The B-CNT shows semiconducting to metallic transition and on introducing the HBr molecule near the surface, changes its conductance drastically. Strong physisorption is observed for HBr over B-CNT surface as a consequence of electrostatic interaction.

We have investigated the electrochemical interface between diamondelectrodes and aqueous electrolytes using electrochemical techniques such as cyclic voltammetry and ac impedance spectroscopy. High-quality CVD-grown boron-doped polycrystalline diamondelectrodes and IIa single crystalline natural diamondelectrodes have been used in this study. In the case of hydrogen-terminated diamondelectrodes, the electrochemical interface is dominated by the electrochemical double layer. Frequency-dependent impedance spectroscopy reveals a potential regime in which the contribution of ion adsorption becomes relevant. We have conducted experiments to evaluate the effect of pH and ionic strength on the double layer. Our results suggest that only ions resulting from water auto-dissociation, i.e., hydroxide and hydronium ions, are responsible for ion adsorption and, thus, able to modify the charge at the double layer. In contrast, no effect of the adsorption of several dissolved ions (such as Na+, K+, Cl-) has been observed On the basis of the electrochemical characterization of H-terminated diamond surfaces, we also discuss the phenomenon of the surface conductivity in diamond, as well as the pH sensitivity of the diamond surface. The influence of the O2/OH- and H2/H3O+ redox couples on the origin of the surface conductivity is discussed.

Full Text Available The electrochemical performances of hydrogen- and oxygen-terminated nano-crystalline diamond film electrodes were investigated by cyclic voltammetry and AC impedance spectroscopy. In addition, the surface morphologies, phase structures, and chemical states of the two diamond films were analysed by scanning probe microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, respectively. The results indicated that the potential window is narrower for the hydrogen-terminated nano-crystalline diamond film than for the oxygen-terminated one. The diamond film resistance and capacitance of oxygen-terminated diamond film are much larger than those of the hydrogen-terminated diamond film, and the polarization resistances and double-layer capacitance corresponding to oxygen-terminated diamond film are both one order of magnitude larger than those corresponding to the hydrogen-terminated diamond film. The electrochemical behaviours of the two diamond film electrodes are discussed.

The introduction of foreign atoms, such as nitrogen, into the hexagonal network of an sp(2)-hybridized carbon atom monolayer has been demonstrated and constitutes an effective tool for tailoring the intrinsic properties of graphene. Here, we report that boron atoms can be efficiently substituted for carbon in graphene. Single-layer graphene substitutionally doped with boron was prepared by the mechanical exfoliation of boron-doped graphite. X-ray photoelectron spectroscopy demonstrated that the amount of substitutional boron in graphite was ~0.22 atom %. Raman spectroscopy demonstrated that the boron atoms were spaced 4.76 nm apart in single-layer graphene. The 7-fold higher intensity of the D-band when compared to the G-band was explained by the elastically scattered photoexcited electrons by boron atoms before emitting a phonon. The frequency of the G-band in single-layer substitutionally boron-doped graphene was unchanged, which could be explained by the p-type borondoping (stiffening) counteracting the tensile strain effect of the larger carbon-boron bond length (softening). Boron-doped graphene appears to be a useful tool for engineering the physical and chemical properties of graphene.

Diamond has always been adored as a jewel. Even more fascinating is its outstanding physical properties; it is the hardest material known in the world with the highest thermal conductivity. Meanwhile, when we turn to its electrical properties, diamond is a rather featureless electrical insulator. However, with borondoping, it becomes a p-type semiconductor, with boron acting as a charge acceptor. Therefore the recent news of superconductivity in heavily boron-dopeddiamond synthesized by hig...

Full Text Available Diamond is a material of interest due to its unique combination of properties, including its chemical inertness and biocompatibility. Polycrystalline diamond (poly-C has been used in experimental biosensors that utilize electrochemical methods and antigen-antibody binding for the detection of biological molecules. Boron-doped poly-C electrodes have been found to be very advantageous for electrochemical applications due to their large potential window, low background current and noise, and low detection limits (as low as 500 fM. The biocompatibility of poly-C is found to be comparable, or superior to, other materials commonly used for implants, such as titanium and 316 stainless steel. We have developed a diamond-based, neural microelectrode-array (MEA, due to the desirability of poly-C as a biosensor. These diamond probes have been used for in vivo electrical recording and in vitro electrochemical detection. Poly-C electrodes have been used for electrical recording of neural activity. In vitro studies indicate that the diamond probe can detect norepinephrine at a 5 nM level. We propose a combination of diamond micro-machining and surface functionalization for manufacturing diamond pathogen-microsensors.

A beautiful jewel of diamond is insulator. However, borondoping can induce semiconductive, metallic and superconducting properties in diamond. When the boron concentration is tuned over 3 × 1020 cm-3, diamonds enter the metallic region and show superconductivity at low temperatures. The metal-insulator transition and superconductivity are analyzed using ARPES, XAS, NMR, IXS, transport and magnetic measurements and so on. This review elucidates the physical properties and mechanism of diamond superconductor as a special superconductivity that occurs in semiconductors.

Recent use of very small photon beams (down to 4 mm) in stereotactic radiotherapy requires new detectors to accurately determine the delivered dose. Diamond detectors have been presented in the literature as an attractive candidate for this application, due to their small detection volume and the diamond atomic number (Z = 6) which is close to water effective atomic number (Zeff ∼ 7.42). However, diamond exhibits a density 3.51 times greater than that of water and recent studies using Monte Carlo simulations have demonstrated the drawback of a high-density detector on small beam output factors. The current study focuses on geometrical parameters of diamond detector, namely, the diamond dimensions and the electrode geometry, in order to solve the dosimetric issues still observed in small photon beams with diamond detectors. To give better insights to these open questions, we have used both computational method and experimental analysis. This study highlighted that reducing diamond dimensions is crucial for small beam output factor measurements and to limit the influence of its high density. Furthermore, electrodes covering the whole diamond surface were essential for a dose rate independence of the diamond detector. The optimal dosimeter derived from this work presented small diamond dimensions of approximately 1 × 1 × 0.15 mm{sup 3}, with diamond-like-carbon electrodes covering the whole diamond surface. A dose rate independence of this diamond detector (better than 0.5% over a wide range of dose rates available on a stereotactic dedicated facility) was obtained due to the electrode geometry. Concerning the output factor measurements, a good agreement (better than 1.1%) was observed between this carbon material detector and two types of passive dosimeters (LiF microcubes and EBT2 radiochromic films) for all beam sizes except the smallest field of 0.6 × 0.6 cm{sup 2} with a deviation of 2.6%. This new study showed the high performance

Full Text Available A study of the mechanical properties of a boron-doped epitaxial polysilicon layer deposited on a Si (100 substrate specimen has been carried out by surface Brillouin scattering at high temperatures. This type of specimen is widely used in micro-electro-mechanical systems (MEMS. By accumulating spectra with the Rayleigh mode and the Lamb continuum the isotropic elastic constants C44 and C11 were obtained, from which the values of the bulk, shear and Young’s moduli and Poisson’s ratio for the layer were determined over a range of temperatures from 20 °C to 110 °C. By contrast, an examination of the literature on polycrystalline silicon shows that other methods each provide a limited range of the above properties and thus additional experiments and techniques were needed. The SBS method is applicable to other polycrystalline materials such as silicon carbide, silicon nitride, silicon germanium and amorphous diamond that have also been used for MEMS applications.

The degradation of diuron and 3,4-dichloroaniline (DCA) has been studied at boron-dopeddiamond (BDD) anode. A three electrode impinging jet cell was used to improve the mass transfer of the reactant to the electrode surface. In the whole range of experimental conditions examined, the reactants were completely mineralised and passivation of the electrode surface was not observed. HPLC and ionic chromatography analyses revealed that the reaction involves the oxidative ring-cleavage and the formation of stoichiometric amounts of chloride and ammonium ions. Depending on the specific experimental conditions, short-chained organic acids were also identified as intermediate products. Values of global current efficiencies greater than 20% were obtained even operating with low reactant concentration (0.17 mM for diuron and 2 mM for dichloroaniline) provided that a suitable ratio between applied current and mass transfer rate was guaranteed.

The degradation of diuron and 3,4-dichloroaniline (DCA) has been studied at boron-dopeddiamond (BDD) anode. A three electrode impinging jet cell was used to improve the mass transfer of the reactant to the electrode surface. In the whole range of experimental conditions examined, the reactants were completely mineralised and passivation of the electrode surface was not observed. HPLC and ionic chromatography analyses revealed that the reaction involves the oxidative ring-cleavage and the formation of stoichiometric amounts of chloride and ammonium ions. Depending on the specific experimental conditions, short-chained organic acids were also identified as intermediate products. Values of global current efficiencies greater than 20% were obtained even operating with low reactant concentration (0.17 mM for diuron and 2 mM for dichloroaniline) provided that a suitable ratio between applied current and mass transfer rate was guaranteed

Highlights: • Nanostructure undoped and borondoped ZnO films were deposited by USP technique. • Influences of doping on the surface and optical properties of the ZnO films were investigated. • XRD spectra of the films exhibited a variation in crystalline quality depending on the B content. - Abstract: ZnO is an II–VI compound semiconductor with a wide direct band gap of 3.3 eV at room temperature. Doped with group III elements (B, Al or Ga), it becomes an attractive candidate to replace tin oxide (SnO{sub 2}) or indium tin oxide (ITO) as transparent conducting electrodes in solar cell devices and flat panel display due to competitive electrical and optical properties. In this work, ZnO and borondoped ZnO (ZnO:B) films have been deposited onto glass substrates at 350 ± 5 °C by a cost-efficient ultrasonic spray pyrolysis technique. The optical, structural, morphological and electrical properties of nanostructure undoped and ZnO:B films have been investigated. Electrical resistivity of films has been analyzed by four-probe technique. Optical properties and thicknesses of the films have been examined in the wavelength range 1200–1600 nm by using spectroscopic ellipsometry (SE) measurements. The optical constants (refractive index (n) and extinction coefficient (k)) and the thicknesses of the films have been fitted according to Cauchy model. The optical method has been used to determine the band gap value of the films. Transmission spectra have been taken by UV spectrophotometer. It is found that both ZnO and ZnO:B films have high average optical transmission (≥80%). X-ray diffraction (XRD) patterns indicate that the obtained ZnO has a hexagonal wurtzite type structure. The morphological properties of the films were studied by atomic force microscopy (AFM). The surface morphology of the nanostructure films is found to depend on the concentration of B. As a result, ZnO:B films are promising contender for their potential use as transparent window layer and

This article reports on the structural, electronic, and optical properties of boron-doped hydrogenated nanocrystalline silicon (nc-Si:H) thin films. The films were deposited by plasma-enhanced chemical vapour deposition (PECVD) at a substrate temperature of 150 deg. C. Crystalline volume fraction and dark conductivity of the films were determined as a function of trimethylboron-to-silane flow ratio. Optical constants of doped and undoped nc-Si:H were obtained from transmission and reflection spectra. By employing p + nc-Si:H as a window layer combined with a p' a-SiC buffer layer, a-Si:H-based p-p'-i-n solar cells on ZnO:Al-coated glass substrates were fabricated. Device characteristics were obtained from current-voltage and spectral-response measurements.

The enhanced diffusivity of oxygen in heavily borondoped silicon was obtained by analyzing oxygen out-diffusion profile changes found at the interface between a lightly boron-doped silicon epitaxial layer and a heavily boron-doped silicon substrate by secondary ion mass spectrometry. It was found that the diffusivity is proportional to the square root of boron concentration in the range of 10{sup 18 }cm{sup −3}–10{sup 19 }cm{sup −3} at temperatures from 750 °C to 950 °C. The model based on the diffusion of oxygen dimers in double positive charge state could explain the enhanced diffusion. We have concluded that oxygen diffusion enhanced in heavily boron-doped silicon is attributed to oxygen dimers ionized depending on Fermi level position.

In this research, catalyst-free vertically aligned borondoped carbon nanowalls films were fabricated on silicon (100) substrates by MPECVD using feeding gases CH4, H2 and B2H6 (diluted with H2 to 5% vol) as precursors. The substrates were pre-seeded with nanodiamond colloid. The fabricated CNWs films were characterized by Scanning Electron Microscopy (SEM) and Raman Spectroscopy. The data obtained from SEM confirms that the CNWs films have different density and wall thickness. From Raman spectrum, a G peak around 1588 cm(-1) and a D band peak at 1362 cm(-1) were observed, which indicates a successful fabrication of CNWs films. The EDX spectrum of borondoped CNWs film shows the existence of boron and carbon. Furthermore, field emission properties of borondoped carbon nanowalls films were measured and field enhancement factor was calculated using Fowler-Nordheim plot. The result indicates that borondoped CNWs films could be potential electron emitting materials.

Highlights: • Plasma carbon and borondoped carbon were formed by vapor phase synthesis using the plasma arc torch. • We investigated that graphite sheets formed as increasing content of boron using the TEM images. • We have confirmed by XRD and Raman analysis that with the increasing amount of boron, carbon increases degree graphtization. • The boron-doped carbons exhibit higher reversible capacity and better rate capability due to improved crystallinity. -- Abstract: Plasma carbon and boron-doped carbons are prepared by gas phase synthesis technique using a plasma arc torch apparatus. The effects of borondoping on the microstructure and electrochemical performance are investigated. Transmission electron microscopy results indicate that crystalline graphitic sheets are formed when the content of boron in the carbon is higher than around 1.00 wt.% X-ray diffraction (XRD) and Raman analysis also reveal that the increased amount of borondoping results in decreased interlayer spacing and increased crystallite size of the boron-doped carbons. The boron-doped carbons exhibit not only higher reversible capacity, but also better rate capability than undoped plasma carbon, due to the formation of nano-structured carbon composite composed of both spherically shaped amorphous (hard carbon-like) and paper-shaped crystalline (graphite-like) phases. The reversible capacity remained over 390 mAh g{sup −1} even after 200 cycles at a current density of 300 mA g{sup −1} for the 1.00 wt.% boron-doped carbon.

Boron-doped carbon nanotubes (B-CNTs) were synthesized using chemical vapour deposition (CVD) floating catalyst method. Toluene was used as the carbon source, triphenylborane as boron as well as the carbon source while ferrocene was used as the catalyst. The amount of triphenylborane used was varied in a solution of toluene and ferrocene. Ferrocene was kept constant at 2.5 wt.%. while a maximum temperature of 900 °C was used for the synthesis of the shaped carbon nanomaterial (SCNMs). SCNMs obtained were characterized by the use of transmission electron microscope (TEM), scanning electron microscope (SEM), high resolution-electron microscope, electron dispersive X-ay spectroscopy (EDX), Raman spectroscopy, inductively coupled plasma-optical emission spectroscopy (ICP-OES), vibrating sample magnetometer (VSM), nitrogen adsorption at 77 K, and inverse gas chromatography. TEM and SEM analysis confirmed SCNMs obtained were a mixture of B-CNTs and carbon nanofibres (B-CNF). EDX and ICP-OES results showed that boron was successively incorporated into the carbon hexagonal network of CNTs and its concentration was dependent on the amount of triphenylborane used. From the VSM results, the borondoping within the CNTs introduced ferromagnetic properties, and as the percentage of boron increased the magnetic coactivity and squareness changed. In addition, borondoping changed the conductivity and the surface energy among other physicochemical properties of B-CNTs. - Highlights: • Boron-doping of carbon nanotubes (CNTs) changes their physiochemical properties. • Amount of boron-doping was dependent on the wt.% of boron precursor used. • Boron-doping changed CNTs surfaces and the distribution of dispersive energy sites. • Boron-doping affected the conductivity and ferromagnetic properties. • Increased boron-doping results in a more favourable interaction with polar probes.

Full Text Available Heavy metal pollution is one of the most serious environmental problems, and regulations are becoming stricter. Many efforts have been made to develop sensors for monitoring heavy metals in the environment. This review aims at presenting the different label-free strategies used to develop electrochemical sensors for the detection of heavy metals such as lead, cadmium, mercury, arsenic etc. The first part of this review will be dedicated to stripping voltammetry techniques, on unmodified electrodes (mercury, bismuth or noble metals in the bulk form, or electrodes modified at their surface by nanoparticles, nanostructures (CNT, graphene or other innovative materials such as boron-dopeddiamond. The second part will be dedicated to chemically modified electrodes especially those with conducting polymers. The last part of this review will focus on bio-modified electrodes. Special attention will be paid to strategies using biomolecules (DNA, peptide or proteins, enzymes or whole cells.

Microprobes are an effective analysis and stimulation tool for neural studies. Analysis can take place in one of two modes; the microprobe may be used to detect or measure chemical indicators within the brain, or, it may be used to detect electrical signals emanating from firing neurons. A polycrystalline diamond based probe provides many potential advantages over probes of other materials. Carbon sp3 bonded diamond exhibits transparency and is a good insulator due to its large band gap (5.5 eV). Diamond is also mechanically versatile due its Young's modulus of ˜1011 Pa. A borondopeddiamondelectrode is advantageous when compared to other electrode materials as it is resistive to fouling and chemically inert. Developing a sound design and fabrication process for the diamond probe has proven to be problematic. In this research, the design, microfabrication and testing of a novel polycrystalline diamond (poly-C) based microprobe, for possible applications in neural prosthesis, are developed and presented for the first time. The associated poly-C micromachining technologies are also developed and discussed in depth. Two types of poly-C probes are realized. One is designed for electrical and the other for electrochemical measurements. The probes utilize undoped poly-C with a resistivity in the range of 105 Ocm as a supporting material, which has a Young's modulus in the range of 400--1,000 GPa and is biocompatible. Borondoped poly-C with a resistivity in the range of 10-3 Ocm is used as an electrode material, which provides a chemically stable surface for both chemical and electrical detections in neural studies. The poly-C electrode capacitance is approximately 87 muF/cm 2, which is small as compared to other metal electrodes. The measured water potential window of the poly-C electrode spans across negative and positive electrode potentials and typical has a total value of 2.2 V in 1M KCl. The smallest detectable concentration of norepinephrine (a neurotransmitter

The influence of the substrate electrochemical pre-treatment in 0.5 mol L{sup -1} H{sub 2}SO{sub 4} on the Pt electrodeposition on boron-dopeddiamond, BDD, film electrodes was investigated. Platinum cannot be electrodeposited on a freshly prepared BDD electrode; however, potentiodynamic cycling or anodic potential steps at short times does activate the electrode. Anodic pre-treatment plays a dual role in the behavior of Pt deposition on BDD surfaces: Pt deposition is increased at short-term anodic pre-treatments, whereas at longer pre-treatment times Pt deposition was inhibited. These facts are explained in terms of wettability changes and passivation of the surface. Conversely, the oxide layer formed in these treatments increases the dispersion level of the catalyst. (author)

The borondoped multi-walled carbon nanotubes (B-MWCNTs) were synthesized by thermal annealing multi-walled carbon nanotubes (MWCNTs) in the presence of boric acid. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) results revealed that the structure of MWCNTs does not be destroyed during the doping process, and X-ray photoelectron spectroscopy (XPS) analysis demonstrated the boron atoms were successfully doped in the structure of MWCNTs. The electrocatalytic properties of B-MWCNTs are characterized by rotating disk electrode (RDE) methods. The results demonstrated that the B-MWCNTs catalyzed oxygen reduction reaction (ORR) in alkaline media by a 2 + 2 electron pathway and it showed good catalytic activity for oxygen evolution reaction (OER) as well

The structures and anode performances of graphitized pristine and boron-doped shot and sponge cokes have been comparatively studied by means of scanning electron microscope (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and galvanostatic measurement. The results show that high degree of graphitization can be obtained by the substituted boron atom in the carbon lattice, and boron in the resultant boron-doped graphites mainly exist in the form of boron carbide and boron substituted in the carbon lattice. Both of boron-doped graphites from shot and sponge cokes obtain discharge capacity of 350 mAh g -1 and coulombic efficiency above 90%. Apart from commonly observed discharge plateau for graphite, boron-doped samples in this study also show a small plateau at ca. 0.06 V. This phenomenon can be explained that Li ion stores in the site to be void-like spaces that are produced by "molecular bridging" between the edge sites of graphene layer stack with a release of boron atoms substituted at the edge of graphene layer. The effect of the amount of boron dopant and graphitization temperature on the anode performance of boron-doped graphite are also investigated in this paper.

We report on the response of metal-less CVD polycrystalline-diamond pixel sensors under β-particles irradiation. A 21×21 array of 0.18×0.18 mm{sup 2} pixels was realized on one side of a 10.0×10.0×0.5 mm{sup 3} polycrystalline diamond substrate by means of laser induced surface graphitization. With the same technique, a large graphite contact, used for detector biasing, was fabricated on the opposite side. A coincidence detecting method was used with two other reference polycrystalline diamond detectors for triggering, instead of commonly used scintillators, positioned in the front and on the back of the sensor-array with respect to the impinging particles trajectory. The collected charge distribution at each pixel was analyzed as a function of the applied bias. No change in the pulse height distribution was recorded by inverting the bias voltage polarity, denoting contacts ohmicity and symmetry. A fairly good pixel response uniformity was obtained: the collected charge most probable value saturates for all the pixels at an electric field strength of about ±0.6 V/μm. Under saturation condition, the average collected charge was equal to =1.64±0.02 fC, implying a charge collection distance of about 285 µm. A similar result, within 2%, was also obtained for 400 MeV electrons at beam test facility at INFN Frascati National Laboratory. Experimental results highlighted that more than 84% of impinging particles involved only one pixel, with no significant observed cross-talk effects.

The effects of N 2 incorporation in Ar/CH 4 plasma on the electrochemical properties and microstructure of ultra-nanocrystalline diamond (UNCD) films are reported. While the electrical conductivity of the films increased monotonously with increasing N 2 content (up to 25%) in the plasma, the electrochemical behavior was optimized for UNCD films grown in (Ar–10% N 2 )/CH 4 plasma. Transmission electron microscopy showed that the main factor resulting in high conductivity in the films was the formation of needle-like nanodiamond grains and the induction graphite layer encapsulating these grains. The electrochemical process for N 2 -incorporated UNCD films can readily be activated due to the presence of nanographite along the grain boundaries of the films. The formation of needle-like diamond grains was presumably due to the presence of CN species that adhered to the existing nanodiamond clusters, which suppressed radial growth of the nanodiamond crystals, promoting anisotropic growth and the formation of needle-like nanodiamond. The N 2 -incorporated UNCD films outperformed other electrochemical electrode materials, such as boron-dopeddiamond and glassy carbon, in that the UNCD electrodes could sense dopamine, urea, and ascorbic acid simultaneously in the same mixture with clear resolution

Beyond conventional electrically-driven neuronal stimulation methods, there is a growing interest in optically-driven approaches. In recent years, nitrogen-doped ultrananocrystalline diamond (N-UNCD) has emerged as a strong material candidate for use in electrically-driven stimulation electrodes. This work investigates the electrochemical activity of N-UNCD in response to pulsed illumination, to assess its potential for use as an optically-driven stimulation electrode. Whilst N-UNCD in the as-grown state exhibits a weak photoresponse, the oxygen plasma treated film exhibits two orders of magnitude enhancement in its sub-bandgap open circuit photovoltage response. The enhancement is attributed to the formation of a dense network of oxygen-terminated diamond nanocrystals at the N-UNCD surface. Electrically connected to the N-UNCD bulk via sub-surface graphitic grain boundaries, these diamond nanocrystals introduce a semiconducting barrier between the sub-surface graphitic semimetal and the electrolyte solution, leading to a photovoltage under irradiation with wavelengths of λ = 450 nm and shorter. Within the safe optical exposure limit of 2 mW mm{sup −2}, charge injection capacity of 0.01 mC cm{sup −2} is achieved using a 15 × 15 μm electrode, meeting the requirements for extracellular and intercellular stimulation. The nanoscale nature of processes presented here along with the diamond's biocompatibility and biostability open an avenue for the use of oxygen treated N-UNCD as optically driven stimulating electrodes.

This conference provided an opportunity for electrochemists, physicists, materials scientists and engineers to meet and exchange information on different carbon allotropes. The presentations and discussion among the participants provided a forum to develop recommendations on research and development which are relevant to the electrochemistry of carbon allotropes. The following topics which are relevant to the electrochemistry of carbon allotropes were addressed: Graphitized and disordered carbons, as Li-ion intercalation anodes for high-energy-density, high-power-density Li-based secondary batteries; Carbons as substrate materials for catalysis and electrocatalysis; Boron-dopeddiamond film electrodes; and Electrochemical characterization and electrosynthesis of fullerenes and fullerene-type materials. Abstracts of the presentations are presented.

was found that chlorobenzene undergoes degradation efficiently in presence of borondoped TiO2 thin films by exposing its aqueous solution to ... at different irradiation times. The solution was bubbled frequently with air during irradiation. ... X-ray diffraction spectra were obtained from an X-ray diffractometer (type PW 3710 ...

report on the synthesis of boron-doped manganese telluride (B-doped MnTe) semiconductor-decorated .... research on this issue represents a stage in the improve- ment to produce higher power conversion efficiency ... sart University, Kamphaeng Saen Campus, for financial support and thanks to the Kasetsart University ...

Abstract. We studied the photovoltaic performance of boron-doped MnTe semiconductor-sensitized solar cells (B-doped MnTe SSCs). The B-doped MnTe semiconductor was grown on ZnO using two stages of the successive ionic layer adsorption and reaction (SILAR) technique. The two phases of B-doped semiconductor.

The role of atomic size of sp-element is investigated through theoretical calculations and basic experiments to understand the physical properties of Borondoped Fe 2 VAl alloy. The results of ab-initio calculations on ordered L2 1 structure of Fe 2 VAl 1-x B x (x=0, 0.5, 1) alloys have been compared to understand the role of sp-element size on the hybridization among their respective valance states. Interestingly, semi-metallic and paramagnetic like ground states were found in the Borondoped alloys in similar to Fe 2 VAl, eliminating the role of size of the doppent sp-atom. These calculations result in hybridization where the covalent distribution of valance states among the atoms is responsible to produce a finite pseudo-gap at the Fermi level. The observed features could be explained on the basis of covalent theory of magnetism in which an amount of spectral weight transfer occurs in the DOS spectrum among the same spin orbitals, leading to symmetric distribution of bonding and anti-bonding states. However, the obtained experimental findings on Borondoped alloys are in contrast with these calculations, indicating that experimentally the alloy formation into an ideal L2 1 lattice does not happen while doping with Boron. Further, the micro structural analysis shows Boron segregation across the grain boundaries that may form magnetic inhomogeneities in the lattice of Borondoped Fe 2 VAl alloys which preferably cause these experimental anomalies

In this work, we presented a novel route to synthesize borondoped reduced graphene oxide (rGO) by using the dielectric barrier discharge (DBD) plasma technology under ambient conditions. The doping of boron (1.4 at%) led to a significant improvement in the capacitance of rGO and supercapacitors...

Heteroatom-doped carbons have been substantially applied on electrochemical applications for their exceptional electrocatalytic ability and electric conductivity. Among the doping elements, electron-deficient boron (B) is considered to be a promising heteroatom for the chemical doping of carbon materials to modify the chemically inert sp2 carbon structure and thus activate the abundant free-flowing π electrons. In this study, B-doped carbon nanotubes (BCNTs) with various borondoping atomic percentages (0.40-3.92 at%) are synthesized and used as a electrocatalyst on the counter electrode (CE) of dye-sensitized solar cells (DSSCs) for investigating the effect of borondoping on carbon materials. A solar-to-electricity conversion efficiency (η) of 7.17 ± 0.11% is achieved for a DSSC with a CE containing BCNTs with optimized B doping concentration (BCNT-0.40 at%), which is higher than that of the cells with CEs consisting of pristine carbon nanotubes (CNT, η = 5.98 ± 0.20%) and is comparable to that of the cell with a Pt CE (η = 7.98 ± 0.05%). It is also noteworthy from a practical viewpoint that the developed atmospheric-pressure synthesis method for synthesizing BCNT is amenable to industrial-scale production since a requirement for vacuum system can be avoided.

The reactions that occur at the interface between an electrode and an electrolyte were examined with particular reference to the interaction of different electrode surfaces with redox couples. A semi-integration or convolution technique was used to study the kinetics of electron transfer on different electrode materials with different hydrophilic behaviour, such as Boron-Doped-Diamond (BDD), Au and Pt. Standard reversible redox couples were also investigated, including (Fe3+/2+, Fe(CN)63-/4-, Ru(NH3)63+/2+, Co(NH3)63+/2+, Ir4+/3+, V4+/5+ and V3+/2+). The proposed method proved to be simple, straightforward and reliable since the obtained kinetic information was in good agreement with data in the literature. It was concluded that the kinetics of the electrode transfer reactions depend on the chemical nature of the redox couple and electrode material. The method should be further extended to irreversible couples and other electrode materials such as mixed oxide electrodes. 3 refs., 2 figs.

The enhanced diffusion of boron has been investigated by analyzing out-diffusion profiles in the vicinity of the interface between a lightly boron-doped silicon epitaxial layer and a heavily boron-doped silicon substrate with a resistivity of 8.2 mΩ cm and an oxide precipitate (O.P.) density of 108-1010 cm-3. It is found that the boron diffusion during annealing at 850-1000 °C is enhanced with the increase of the oxide precipitate density. On the basis of a model for boron diffusion mediated by silicon self-interstitials, we reveal that the enhanced diffusion is attributed to self-interstitials supersaturated as a result of the emission from oxide precipitates and the absorption by punched-out dislocations. In addition, the temperature dependence of the fraction of the self-interstitial emission obtained analyzing the diffusion enhancement well explains the morphology changes of oxide precipitates reported in literature.

Porous diamond-like carbon (DLC) electrodes have been prepared, and their electrochemical performance was explored. For electrode preparation, a thin DLC film was deposited onto a densely packed forest of highly porous, vertically aligned multiwalled carbon nanotubes (VACNT). DLC deposition caused the tips of the carbon nanotubes to clump together to form a microstructured surface with an enlarged surface area. DLC:VACNT electrodes show fast charge transfer, which is promising for several electrochemical applications, including electroanalysis. DLC:VACNT electrodes were applied to the determination of targeted molecules such as dopamine (DA) and epinephrine (EP), which are neurotransmitters/hormones, and acetaminophen (AC), an endocrine disruptor. Using simple and low-cost techniques, such as cyclic voltammetry, analytical curves in the concentration range from 10 to 100 μmol L(-1) were obtained and excellent analytical parameters achieved, including high analytical sensitivity, good response stability, and low limits of detection of 2.9, 4.5, and 2.3 μmol L(-1) for DA, EP, and AC, respectively.

Full Text Available A novel Cu and borondoped graphitic carbon nitride catalyst (Cu-CNB was synthesized using cheap precursors and systematically characterized. The selective oxidation of toluene proceeded very smoothly over the catalyst at 70 °C using tert-butyl hydroperoxide (TBHP as the oxidant to exclusively afford benzaldehyde. The catalyst can be used for at least five cycles without decrease in activity and selectivity.

We report fully quantum simulations of realistic models of boron-doped graphene-based field-effect transistors, including atomistic details based on DFT calculations. We show that the self-consistent solution of the three-dimensional (3D) Poisson and Schrödinger equations with a representation in terms of a tight-binding Hamiltonian manages to accurately reproduce the DFT results for an isolated boron-doped graphene nanoribbon. Using a 3D Poisson/Schrödinger solver within the non-equilibrium Green's function (NEGF) formalism, self-consistent calculations of the gate-screened scattering potentials induced by the boron impurities have been performed, allowing the theoretical exploration of the tunability of transistor characteristics. The boron-doped graphene transistors are found to approach unipolar behavior as the boron concentration is increased and, by tuning the density of chemical dopants, the electron-hole transport asymmetry can be finely adjusted. Correspondingly, the onset of a mobility gap in the device is observed. Although the computed asymmetries are not sufficient to warrant proper device operation, our results represent an initial step in the direction of improved transfer characteristics and, in particular, the developed simulation strategy is a powerful new tool for modeling doped graphene nanostructures.

The intercalation of a graphene layer adsorbed on a metal surface by gold or other metals is a standard procedure. While it was previously shown that pristine, i.e., undoped, and nitrogen-doped graphene sheets can be decoupled from a nickel substrate by intercalation with gold atoms in order to produce quasi-free-standing graphene, we find the gold intercalation behavior for boron-doped graphene on a Ni(111) surface to be more complex: for low boron contents (2-5%) in the graphene lattice only partial gold intercalation occurs and for higher boron contents (up to 20%) no intercalation is observed. In order to understand this different behavior, a density functional theory investigation is carried out, comparing undoped as well as substitutional nitrogen- and boron-doped graphene on Ni(111). We identify the stronger binding of the boron atoms to the nickel substrate as the factor responsible for the different intercalation behavior in the case of borondoping. However, the calculations predict that this energetic effect prevents the intercalation process only for large boron concentrations and that it can be overcome for smaller boron coverages, in line with our x-ray photoelectron spectroscopy experiments.

Boron-doping of activated carbons has been shown to increase the enthalpies of adsorption for hydrogen as compared to their respective undoped precursors (>10kJ/mol compared to ca. 5kJ/mol). This has brought significant interest to boron-doped carbons for their potential to improve hydrogen storage. Boron-doped activated carbons have been produced using a process involving the deposition of decaborane (B10H14) and high-temperature annealing resulting in boron contents up to 15%. In this talk, we will present a systematic study of the effect that boron content has on the samples' structure, hydrogen sorption, and surface chemistry. Measurements have shown a significant increase in the areal hydrogen excess adsorption and binding energy. Experimental enthalpies of adsorption will be presented for comparison to theoretical predictions. Additionally, samples have been characterized by thermal gravimetric analysis, gas chromatography-mass spectroscopy, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. TGA and GC-MS results investigated the decomposition of the decaborane in the carbon. Boron-carbon bonds are shown in the FTIR and XPS spectra, indicating that boron has been incorporated into the carbon matrix. Work supported by DOE-EERE, Award No. DE-FG36-08GO18142

There is significant interest in the properties of boron-doped activated carbons for their potential to improve hydrogen storage. Boron-doped activated carbons have been produced using a novel process involving the pyrolysis of a boron containing compound and subsequent high-temperature annealing. In this talk we will present a systematic study of the effect of different borondoping processes on the samples' surface area, micropore structure, and hydrogen sorption. Experimental results include boron content from prompt gamma neutron activation analysis, boron-carbon chemistry from Fourier transform infrared spectroscopy (FTIR), nitrogen subcritical adsorption, and 80K and 90K hydrogen adsorption isotherms which allow us to evaluate the hydrogen binding energy for each sorptive material. This material is based on work supported by the US Department of Defense under Awards No. N00164-07-P-1306 and N00164-08-C-GS37, the US Department of Energy under Awards No. DE-FG02-07ER46411 and DE-FG36-08GO18142.

Full Text Available Cadmium(II is a common water pollutant with high toxicity. It is of significant importance for detecting aqueous contaminants accurately, as these contaminants are harmful to human health and environment. This paper describes the fabrication, characterization, and application of an environment-friendly graphene (Gr/l-cysteine/gold electrode to detect trace levels of cadmium (Cd by differential pulse stripping voltammetry (DPSV. The influence of hydrogen overflow was decreased and the current response was enhanced because the modified graphene extended the potential range of the electrode. The Gr/l-cysteine/gold electrode showed high electrochemical conductivity, producing a marked increase in anodic peak currents (vs. the glass carbon electrode (GCE and boron-dopeddiamond (BDD electrode. The calculated detection limits are 1.15, 0.30, and 1.42 µg/L, and the sensitivities go up to 0.18, 21.69, and 152.0 nA·mm−2·µg−1·L for, respectively, the BDD electrode, the GCE, and the Gr/l-cysteine/gold electrode. It was shown that the Gr/l-cysteine/gold-modified electrode is an effective means for obtaining highly selective and sensitive electrodes to detect trace levels of cadmium.

This article has been retracted: please see Elsevier Policy on Article Withdrawal (http://www.elsevier.com/locate/withdrawalpolicy). This article has been retracted at the request of the Principal Editor. After a thorough investigation, the Editor has concluded that the review process for this article was compromised. The acceptance was based on information from one reviewer report that was submitted from an email account provided to the journal as a suggested reviewer during the submission of the article. Although purportedly a real reviewer account, the Editor has concluded that this was not of an appropriate, independent reviewer. This manipulation of the peer-review process represents a clear violation of the fundamentals of peer review, our publishing policies, and publishing ethics standards. Apologies are offered to the reviewer whose identity was assumed and to the readers of the journal that this deception was not detected during the submission process.

Boron-dopeddiamond is a material with a great technological and industrial interest because of its exceptional chemical, physical and structural properties. At modest boron concentrations, insulating diamond becomes a p-type semiconductor and at higher concentrations a superconducting metal at low temperature. The most conventional preparation method used so far, has been the homogeneous incorporation of borondoping during the diamond synthesis carried out either with high-pressure sintering of crystals or by chemical vapour deposition (CVD) of films. With these methods, high boron concentration can be included without distorting significantly the diamond crystalline lattice. However, it is complicated to manufacture boron-doped microstructures. A promising alternative to produce such microstructures could be the implantation of focused high-energy boron ions, although boron fluences are limited by the damage produced in diamond. In this work, the effect of focused high-energy boron ion implantation in single crystals of diamond is studied under different irradiation fluences and conditions. Micro-Raman spectra of the sample were measured before and after annealing at 1000 °C as a function of irradiation fluence, for both superficial and buried boron implantation, to assess the changes in the diamond lattice by the creation of vacancies and defects and their degree of recovery after annealing.

The growth of highly conductive borondoped microcrystalline silicon by the hot wire method was studied. Various series of films were deposited to investigate the influence of the deposition parameters on conductivity, crystallinity and (void-related) microstructure. Maximum (room temperature) conductivities > 200 S/cm with carrier mobilities > 2.5 cm{sup 2}/Vs were achieved. While a high crystallinity is the major requirement for achieving high conductivities, the microstructure is also of influence. (copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Thermal management remains one of the major challenges in the design of safe and reliable Li-ion batteries. We show that composite electrodes assembled from commercially available 100 μm long carbon nanotubes (CNTs) and LiCoO2 (LCO) particles demonstrate the in-plane thermal conductivity of 205.8 W/m*K. This value exceeds the thermal conductivity of dry conventional laminated electrodes by about three orders of magnitude. The cross-plane thermal conductivity of CNT-based electrodes is in the same range as thermal conductivities of conventional laminated electrodes. The CNT-based electrodes demonstrate a similar capacity to conventional laminated design electrodes, but revealed a better rate performance and stability. The introduction of diamond particles into CNT-based electrodes further improves the rate performance. Our lightweight, flexible electrode design can potentially be a general platform for fabricating polymer binder- and aluminum and copper current collector- free electrodes from a broad range of electrochemically active materials with efficient thermal management.

The boron-dopeddiamond (BDD) thin-film electrode with high quality using industrially titanium plate (Ti/BDD) as substrate has been prepared and firstly used in the oxidation of anthraquinone dye Alizarin Red S (ARS) in wastewaters. The Ti/BDD electrodes are shown to have high concentration of sp{sup 3}-bonded carbon and wide electrochemical window. The results of the cyclic voltammetries show that BDD has unique properties such as high anodic stability and the production of active intermediates at the high potential. The oxidation regions of ARS and water are significantly separated at the Ti/BDD electrode, and the peak current increases linearly with increasing ARS concentration. The bulk electrolysis shows that removal of chemical oxygen demand (COD) and color can be completely reached and the electrooxidation of ARS behaves as a mass-transfer-controlled process at the Ti/BDD electrode. It is demonstrated that the performances of the Ti/BDD electrode for anodic oxidation ARS have been significantly improved with respect to the traditional electrodes.

Reduction of dioxygen catalyzed by laccase was studied at carbon electrodes without any added mediators. On bare glassy carbon electrode (GCE) the catalytic reduction did not take place. However, when the same substrate was decorated with carbon nanotubes or carbon microcrystals the dioxygen reduction started at 0.6 V versus Ag/AgCl, which is close to the formal potential of the laccase used. Four different matrices: lecithin, hydrophobin, Nafion and lipid liquid-crystalline cubic phase were employed for hosting fungal laccase from Cerrena unicolor. The carbon nanotubes and nanoparticles present on the electrode provided electrical connectivity between the electrode and the enzyme active sites. Direct electrochemistry of the enzyme itself was observed in deoxygenated solutions and its catalytic activity towards dioxygen reduction was demonstrated. The stabilities of the hosted enzymes, the reduction potentials and ratios of catalytic to background currents were compared. The boron-dopeddiamond (BDD) electrodes prepolarized to high anodic potentials exhibited behavior similar to that of nanotube covered GCE pointing to the formation of nanostructures during the anodic pretreatment. BDD is a promising substrate in terms of potential of dioxygen reduction, however the catalytic current densities are not large enough for practical applications, therefore as shown in this paper, it should be additionally decorated with carbon particles being in direct contact with the electrode surface.

The electrochemical oxidation of Ibuprofen (Ibu) was performed using a Ti/Pt/PbO 2 electrode as the anode, prepared according to literature, and a borondopeddiamond (BDD) electrode, commercially available at Adamant Technologies. Tests were performed with model solutions of Ibu, with concentrations ranging from 0.22 to 1.75 mM for the Ti/Pt/PbO 2 electrode and 1.75 mM for the BDD electrode, using 0.035 M Na 2 SO 4 as the electrolyte, in a batch cell, at different current densities (10, 20 and 30 mA cm -2 ). Absorbance measurements, Chemical Oxygen Demand (COD) and Total Organic Carbon (TOC) tests were conducted for all samples. The results have shown a very good degradation of Ibu, with COD removals between 60 and 95% and TOC removals varying from 48 to 92%, in 6 h experiments, with higher values obtained with the BDD electrode. General Current Efficiency and Mineralization Current Efficiency, determined for both electrodes, show a similar behaviour for 20 mA cm -2 but a very different one at 30 mA cm -2 . The combustion efficiency was also determined for both anodes, and found to be slightly higher with BDD at lower current density and equal to 100% for both anodes at 30 mA cm -2

Full Text Available The detection of quantal exocytic events from neurons and neuroendocrine cells is a challenging task in neuroscience. One of the most promising platforms for the development of a new generation of biosensors is diamond, due to its biocompatibility, transparency and chemical inertness. Moreover, the electrical properties of diamond can be turned from a perfect insulator into a conductive material (resistivity ~mΩ·cm by exploiting the metastable nature of this allotropic form of carbon. A 16‑channels MEA (Multi Electrode Array suitable for cell culture growing has been fabricated by means of ion implantation. A focused 1.2 MeV He+ beam was scanned on a IIa single-crystal diamond sample (4.5 × 4.5 × 0.5 mm3 to cause highly damaged sub-superficial structures that were defined with micrometric spatial resolution. After implantation, the sample was annealed. This process provides the conversion of the sub-superficial highly damaged regions to a graphitic phase embedded in a highly insulating diamond matrix. Thanks to a three-dimensional masking technique, the endpoints of the sub-superficial channels emerge in contact with the sample surface, therefore being available as sensing electrodes. Cyclic voltammetry and amperometry measurements of solutions with increasing concentrations of adrenaline were performed to characterize the biosensor sensitivity. The reported results demonstrate that this new type of biosensor is suitable for in vitro detection of catecholamine release.

The study of protein adsorption on solid surfaces is interesting for theoretical and practical bio-analytical sensing applications. In this work we combine electrochemical impedance spectroscopy, enzyme linked immunosorbent assay, and fluorescence microscopy with thin borondoped nanocrystalline diamond films to address and study the adsorption behavior of globular proteins (antibodies) on hydrophobic and hydrophilic diamond surfaces. A powerful combination of time resolved impedance spectros...

Full Text Available The addition of aluminum to silver metallization pastes has been found to lower the contact resistivity of a silver metallization on boron-doped silicon emitters for n-type Si solar cells. However, the addition of Al also induces more surface recombination and increases the Ag pattern′s line resistivity, both of which ultimately limit the cell efficiency. There is a need to develop a fundamental understanding of the role that Al plays in reducing the contact resistivity and to explore alternative additives. A fritless silver paste is used to allow direct analysis of the impact of Al on the Ag-Si interfacial microstructure and isolate the influence of Al on the electrical contact from the complicated Ag-Si interfacial glass layer. Electrical analysis shows that in a simplified system, Al decreases the contact resistivity by about three orders of magnitude. Detailed microstructural studies show that in the presence of Al, microscale metallic spikes of Al-Ag alloy and nanoscale metallic spikes of Ag-Si alloy penetrate the surface of the boron-doped Si emitters. These results demonstrate the role of Al in reducing the contact resistivity through the formation of micro- and nano-scale metallic spikes, allowing the direct contact to the emitters.

Serotonin (5-HT) is an important neurochemical that is present in high concentrations within the intestinal tract. Carbon fibre and boron-dopeddiamond based electrodes have been widely used to date for monitoring 5-HT, however these electrodes are prone to fouling and are difficult to fabricate in certain sizes and geometries. Carbon nanotubes have shown potential as a suitable material for electroanalytical monitoring of 5-HT but can be difficult to manipulate into a suitable form. The fabrication of composite electrodes is an approach that can shape conductive materials into practical electrode geometries suitable for biological environments. This work investigated how compression of multiwall carbon nanotubes (MWCNTs) epoxy composite electrodes can influence their electroanalytical performance. Highly compressed composite electrodes displayed significant improvements in their electrochemical properties along with decreased internal and charge transfer resistance, reproducible behaviour and improved batch to batch variability when compared to non-compressed composite electrodes. Compression of MWCNT epoxy composite electrodes resulted in an increased current response for potassium ferricyanide, ruthenium hexaammine and dopamine, by preferentially removing the epoxy during compression and increasing the electrochemical active surface of the final electrode. For the detection of serotonin, compressed electrodes have a lower limit of detection and improved sensitivity compared to non-compressed electrodes. Fouling studies were carried out in 10 μM serotonin where the MWCNT compressed electrodes were shown to be less prone to fouling than non-compressed electrodes. This work indicates that the compression of MWCNT carbon-epoxy can result in a highly conductive material that can be moulded to various geometries, thus providing scope for electroanalytical measurements and the production of a wide range of analytical devices for a variety of systems

We investigated the influence of borondoping on the structural, optical, and electrical properties of copper tin sulfide (CTS) nanoparticles coated on a WO3 surface and synthesized using chemical bath deposition. Borondoping at concentrations of 0.5, 1.0, 1.5, and 2.0 wt% was investigated. The X-ray diffraction pattern of CTS showed the presence of monoclinic Cu2Sn3S7, cubic Cu2SnS3, and orthorhombic Cu4SnS4. Borondoping influenced the preferred orientation of the nanoparticles for all phase structures and produced a lattice strain effect and changes in the dislocation density. Increasing the concentration of boron in CTS from 0.5 wt% to 2.0 wt% reduced the band gap for all phases of CTS from 1.46 to 1.29 eV and reduced the optical transmittance. Optical constants, such as the refractive index, extinction coefficient, and dissipation factor, were also obtained for B-doped CTS. The dispersion behavior of the refractive index was investigated in terms of a single oscillator model and the physical parameters were determined. Fourier transform infrared spectroscopy confirmed the successful synthesis of CTS nanoparticles. Cyclic voltammetry indicated that optimum borondoping (<1.5 wt% for all phases) resulted in desirable p-n junction behavior for optoelectronic applications.

To analyze the local structure and/or chemical states of boron atoms in boron-dopeddiamond, which can be synthesized by the microwave plasma-assisted chemical vapor deposition method (CVD-B-diamond) and the temperature gradient method at high pressure and high temperature (HPT-B-diamond), we measured the soft X-ray emission spectra in the CK and BK regions of B-diamonds using synchrotron radiation at the Advanced Light Source (ALS). X-ray spectral analyses using the fingerprint method and mo...

This paper presents the application of a multiscale field theory in modeling and simulation of boron-doped nanocrystalline silicon carbide (B-SiC). The multiscale field theory was briefly introduced. Based on the field theory, numerical simulations show that intergranular glassy amorphous films (IGFs) and nano-sized pores exist in triple junctions of the grains for nanocrystalline B-SiC. Residual tensile stress in the SiC grains and compressive stress on the grain boundaries (GBs) were observed. Under tensile loading, it has been found that mechanical response of 5 wt% boron-SiC exhibits five characteristic regimes. Deformation mechanism at atomic scale has been revealed. Tensile strength and Young's modulus of nanocrystalline SiC were accurately reproduced.

This project, since its start in 2007—entitled “Networks of boron-doped carbon nanopores for low-pressure reversible hydrogen storage” (2007-10) and “New pathways and metrics for enhanced, reversible hydrogen storage in boron-doped carbon nanospaces” (2010-13)—is in support of the DOE's National Hydrogen Storage Project, as part of the DOE Hydrogen and Fuel Cells Program’s comprehensive efforts to enable the widespread commercialization of hydrogen and fuel cell technologies in diverse sectors of the economy. Hydrogen storage is widely recognized as a critical enabling technology for the successful commercialization and market acceptance of hydrogen powered vehicles. Storing sufficient hydrogen on board a wide range of vehicle platforms, at energy densities comparable to gasoline, without compromising passenger or cargo space, remains an outstanding technical challenge. Of the main three thrust areas in 2007—metal hydrides, chemical hydrogen storage, and sorption-based hydrogen storage—sorption-based storage, i.e., storage of molecular hydrogen by adsorption on high-surface-area materials (carbons, metal-organic frameworks, and other porous organic networks), has emerged as the most promising path toward achieving the 2017 DOE storage targets of 0.055 kg H2/kg system (“5.5 wt%”) and 0.040 kg H2/liter system. The objective of the project is to develop high-surface-area carbon materials that are boron-doped by incorporation of boron into the carbon lattice at the outset, i.e., during the synthesis of the material. The rationale for boron-doping is the prediction that boron atoms in carbon will raise the binding energy of hydro- gen from 4-5 kJ/mol on the undoped surface to 10-14 kJ/mol on a doped surface, and accordingly the hydro- gen storage capacity of the material. The mechanism for the increase in binding energy is electron donation from H2 to electron-deficient B atoms, in the form of sp2 boron-carbon bonds. Our team is proud to have

Full Text Available Recently, the capture and storage of CO2 have attracted research interest as a strategy to reduce the global emissions of greenhouse gases. It is crucial to find suitable materials to achieve an efficient CO2 capture. Here we report our study of CO2 adsorption on boron-doped C60 fullerene in the neutral state and in the 1e−-charged state. We use first principle density functional calculations to simulate the CO2 adsorption. The results show that CO2 can form weak interactions with the BC59 cage in its neutral state and the interactions can be enhanced significantly by introducing an extra electron to the system.

We have investigated the magnetic behavior of Fe{sub 2}VAl{sub 1−x}B{sub x} (x=0, 0.03, 0.06 and 0.1) alloys under high temperature and high magnetic field conditions separately. Although, the low temperature DC magnetization data for the alloys above x>0 show clear magnetic transitions, the zero field cooled (ZFC) and field cooled (FC) curves indicate the presence of spin cluster like features. Further, critical exponent (γ) deduced from the initial susceptibility above the T{sub c}, does not agree with standard models derived for 3 dimensional long range magnetic systems. The deviation in γ values are consistent with the short range magnetic nature of these alloys. We further extend the analysis of magnetic behavior by carrying the magnetization measurements at high temperatures and high magnetic fields distinctly. We mainly emphasize the following observations; (i) The magnetic hysteresis loops show sharp upturns at lower fields even at 900 K for all the alloys. (ii) High temperature inverse susceptibility do not overlap until T=900 K, indicating the persistent short range magnetic correlations even at high temperatures. (iii) The Arrott's plot of magnetization data shows spontaneous moment (M{sub S}) for the x=0 alloy at higher magnetic fields which is absent at lower fields (<50 kOe), while the Borondoped samples show feeble M{sub S} at lower fields. The origin of this short range correlation is due to presence of dilute magnetic heterogeneous phases which are not detected from the X-ray diffraction method. - Highlights: • Short range magnetic character has been confirmed by the critical exponents analysis. • Magnetoresistace is about −14% with non-saturating tendency even at 150 kOe for Fe{sub 2}VAl alloy. • Borondoped Fe{sub 2}VAl alloys show a weak magnetism even at T=900 K.

Experimental and modeling studies of the gas-phase chemistry occurring in dilute, hot filament (HF) activated B 2 H 6 /CH 4 /H 2 gas mixtures appropriate for growth of boron-dopeddiamond are reported. The results of two-dimensional modeling of heat and mass transfer processes and the B/H/C chemistry prevailing in such HF activated gas mixtures (supplemented by reactions involving trace O 2 present as air impurity in the process gas mixture) are discussed and compared with measurements of B atom densities as functions of the hot wire temperature T w and distance from the wire. Most of the B 2 H 6 molecules that diffuse from the cool, near-wall regions into the hot, near wire region are thermally decomposed (yielding two BH 3 molecules as primary products) and then converted into various 'active' B-containing species like B, BH and BH 2 - some of which are able to accommodate into the growing diamond film. H-shifting reactions BH x + H ↔ BH x-1 + H 2 enable rapid inter-conversion between the various BH x (x = 0-3) species and the BH x source is limited by diffusional transfer of B 2 H 6 . H atoms play several key roles - e.g. activating the process gas mixture, and driving inter-conversions between the various H x B y C z O z' species. We show that the T w and gas pressure dependences of the H atom production rate (by H 2 dissociation on the HF surface) can be accommodated by a simple gas-surface reaction model.

To analyze the local structure and/or chemical states of boron atoms in boron-dopeddiamond, which can be synthesized by the microwave plasma-assisted chemical vapor deposition method (CVD-B-diamond) and the temperature gradient method at high pressure and high temperature (HPT-B-diamond), we measured the soft X-ray emission spectra in the CK and BK regions of B-diamonds using synchrotron radiation at the Advanced Light Source (ALS). X-ray spectral analyses using the fingerprint method and molecular orbital calculations confirm that boron atoms in CVD-B-diamond substitute for carbon atoms in the diamond lattice to form covalent B-C bonds, while boron atoms in HPT-B-diamond react with the impurity nitrogen atoms to form hexagonal boron nitride. This suggests that the high purity diamond without nitrogen impurities is necessary to synthesize p-type B-diamond semiconductors.

Full Text Available The Atmospheric Pressure Chemical Vapor Synthesis (APCVS route is a process that can be used for the synthesis of doped-nanocrystalline powders with very small crystallite sizes having a narrow particle size distribution and high purity. In this study, APCVS technique was used to prepare boron-doped titania nanopowders. The effects of temperature, borate flow rate and water flow rate on the amount of doped boron were studied. The resultant powders were characterized by inductively coupled plasma (ICP, X-ray diffraction (XRD, nitrogen adsorption technique (BET, UV-visible DRS spectroscopy, scanning electron microscopy (SEM, and transmission electron microscopy (TEM. The optimum boron precursor flow rate was 80 sccm. The highest amount of doped boron was attained when water flow rate was 900 sccm. In comparison to the pristine TiO2, the boron-doped TiO2 nanoparticles showed blue-shift in band-gap energy of the samples.

To improve the electrochemical performance of the high energy Li–O2 batteries, it is important to design and construct a suitable and effective oxygen-breathing cathode. Herein, a three-dimensional (3D) porous boron-doped reduction graphite oxide (B-rGO) material with a hierarchical structure has been prepared by a facile freeze-drying method. In this design, boric acid as the boron source helps to form the 3D porous structure, owing to its cross-linking and pore-forming function. This architecture facilitates the rapid oxygen diffusion and electrolyte penetration in the electrode. Meanwhile, the boron–oxygen functional groups linking to the carbon surface or edge serve as additional reaction sites to activate the ORR process. It is vital that boron atoms have been doped into the carbon lattices to greatly activate the electrons in the carbon π system, which is beneficial for fast charge under large current densities. Density functional theory calculation demonstrates that B-rGO exhibits much stronger interactions with Li5O6 clusters, so that B-rGO more effectively activates Li–O bonds to decompose Li2O2 during charge than rGO does. With B-rGO as a catalytic substrate, the Li–O2 battery achieves a high discharge capacity and excellent rate capability. Moreover, catalysts could be added into the B-rGO substrate to further lower the overpotential and enhance the cycling performance in future.

Diamond film electrode has been known as a material with very wide potential window for water electrolysis which leads to its applicability in numerous electrochemical processes. Its capability to produce hydroxyl radicals, a very strong oxidants, prompts its popular application in wastewater treatment. Batch and batch recirculation reactor were applied to perform bulk electrolysis experiments to investigate the kinetics of dye decolorization under different operation conditions, such as pH, active species, and current density. Furthermore, COD degradation data from batch recirculation reactor operation was used as the basis for the calculation of current efficiency and power consumption in the decolorization process. The kinetics of decolorization process using boron-doped nanocrystalline diamond (BD-NCD) film electrode revealed that acidic condition is favored for the dye degradation, and the presence of chloride ion in the solution was found to be more advantageous than sulfate active species, as evidenced by the higher reaction rate constants. Applying different current density of 10, 20 and 30 mA cm-2, it was found that the higher the current density the faster the decolorization rate. General current efficiency achieved after nearly total decolorization and 80% COD removal in batch recirculation reactor was around 74%, with specific power consumption of 4.4 kWh m-3 (in terms of volume of solution treated) or 145 kWh kg-1(in terms of kg COD treated).

Full Text Available Motivated by the idea of impurity band superconductivity in heavily Borondopeddiamond, we investigate the doping of various elements into diamond to address the question, which impurity band can offer a better DOS at the Fermi level. Surprisingly, we find that the vacancy does the best job in producing the largest DOS at the Fermi surface. To investigate the effect of disorder in Anderson localization of the resulting impurity band, we use a simple tight-binding model. Our preliminary study based on the kernel polynomial method shows that the impurity band is already localized at the concentration of 10-3. Around the vacancy concentration of 0.006 the whole spectrum of diamond becomes localized and quantum percolation takes place. Therefore to achieve conducting bands at concentrations on the scale of 5-10 percent, one needs to introduce correlations such as hopping among the vacancies .

In-situ borondoping of CdS using chemical-bath deposition (CBD) is reported. The effect of B doping on optical properties, as well as electrical properties, crystal structure, chemistry, and morphology of CdS films is studied. We present a successful approach towards B doping of CdS using CBD, where a resistivity as low as 1.7 x 10 -2 Ωcm and a carrier density as high as 1.91 x 10 19 cm -3 were achieved. The bandgap of B-doped films was found to slightly decrease as the[B]/[Cd] ratio in the solution increases. X-ray diffraction studies showed B 3+ ions likely enter the lattice substitutionally. A phase transition, due to annealing, as well as induced lattice defects, due to B doping, were detected by micro-Raman spectroscopy and transmission electron microscopy. The chemistry and morphology of films were unaffected by B doping. (copyright 2009 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

First principles modeling of nitrogen- and boron-doped phosphorene demonstrates the tendency toward the formation of highly ordered structures. Nitrogen doping leads to the formation of -N-P-P-P-N- lines. Further transformation into -P-N-P-N- lines across the chains of phosphorene occurs with increasing band gap and increasing nitrogen concentration, which coincides with the decreasing chemical activity of N-doped phosphorene. In contrast to the case of nitrogen, boron atoms prefer to form -B-B- pairs with the further formation of -P-P-B-B-P-P- patterns along the phosphorene chains. The low concentration of boron dopants converts the phosphorene from a semiconductor into a semimetal with the simultaneous enhancement of its chemical activity. Co-doping of phosphorene by both boron and nitrogen starts from the formation of -B-N- pairs, which provides flat bands and further transformation of these pairs into hexagonal BN lines and ribbons across the phosphorene chains.

Boron-doped titanium dioxide (B-TiO2) films were deposited by atmospheric pressure chemical vapour deposition of titanium(iv) chloride, ethyl acetate and tri-isopropyl borate on steel and fluorine-doped-tin oxide substrates at 500, 550 and 600 °C, respectively. The films were characterised using powder X-ray diffraction (PXRD), which showed anatase phase TiO2 at lower deposition temperatures (500 and 550 °C) and rutile at higher deposition temperatures (600 °C). X-ray photoelectron spectroscopy (XPS) showed a dopant level of 0.9 at% B in an O-substitutional position. The ability of the films to reduce water was tested in a sacrificial system using 365 nm UV light with an irradiance of 2 mW cm(-2). Hydrogen production rates of B-TiO2 at 24 μL cm(-2) h(-1) far exceeded undoped TiO2 at 2.6 μL cm(-2) h(-1). The B-TiO2 samples were also shown to be active for water oxidation in a sacrificial solution. Photocurrent density tests also revealed that B-doped samples performed better, with an earlier onset of photocurrent.

The implementation of future graphene-based electronics is essentially restricted by the absence of a band gap in the electronic structure of graphene. Options of how to create a band gap in a reproducible and processing compatible manner are very limited at the moment. A promising approach for the graphene band gap engineering is to introduce a large-scale sublattice asymmetry. Using photoelectron diffraction and spectroscopy we have demonstrated a selective incorporation of boron impurities into only one of the two graphene sublattices. We have shown that in the well-oriented graphene on the Co(0001) surface the carbon atoms occupy two nonequivalent positions with respect to the Co lattice, namely top and hollow sites. Boron impurities embedded into the graphene lattice preferably occupy the hollow sites due to a site-specific interaction with the Co pattern. Our theoretical calculations predict that such boron-doped graphene possesses a band gap that can be precisely controlled by the dopant concentration. B-graphene with doping asymmetry is, thus, a novel material, which is worth considering as a good candidate for electronic applications.

The adsorption of dibenzothiophene (DBT) on bare and boron-doped armchair carbon nanoribbons (ACNRs) is being investigated in the framework of the density functional theory by implementing periodic boundary conditions that include corrections from dispersion interactions. The reactivity of the ACNRs is characterized by using the Fukui functions as well as the electrostatic potential as local descriptors. Non-covalent adsorption mechanism is found when using the local Perdew-Becke-Ernzerhof functional, regardless of the DBT orientation and adsorption location. The dispersion interactions addition is a milestone to describe the adsorption process. The charge defects introduced in small number (i.e., by doping with B atoms), within the ACNRs increases the selectivity towards sulfur mainly due to the charge depletion at B sites. The DBT magnitude in the adsorption energy shows non-covalent interactions. As a consequence, the configurations where the DBT is adsorbed on a BC{sub 3} island increase the adsorption energy compared to random B arrangements. The stability of these configurations can be explained satisfactorily in terms of dipole interactions. Nevertheless, from the charge-density difference analysis and the weak Bader charge-distribution interactions cannot be ruled out completely. This is why the electronic properties of the ribbons are analyzed in order to elucidate the key role played by the B and DBT states in the adsorbed configurations.

Full Text Available Microstructure curvature, or buckling, is observed in the micromachining of silicon sensors because of the doping of impurities for realizing certain electrical and mechanical processes. This behavior can be a key source of error in inertial sensors. Therefore, identifying the factors that influence the buckling value is important in designing MEMS devices. In this study, the curvature in the proof mass of an accelerometer is modeled as a multilayered solid model. Modeling is performed according to the characteristics of the solid diffusion mechanism in the bulk-dissolved wafer process (BDWP based on the self-stopped etch technique. Moreover, the proposed multilayered solid model is established as an equivalent composite structure formed by a group of thin layers that are glued together. Each layer has a different Young’s modulus value and each undergoes different volume shrinkage strain owing to borondoping in silicon. Observations of five groups of proof mass blocks of accelerometers suggest that the theoretical model is effective in determining the buckling value of a fabricated structure.

The solar industry has grown immensely in recent years and has reached a point where solar energy has now become inexpensive enough that it is starting to emerge as a mainstream electrical generation source. However, recent economic analysis has suggested that for solar to become a truly wide spread source of electricity, the costs still need to plummet by a factor of 8x. This demands new and innovative concepts to help lower such cost. In pursuit of this goal, this dissertation examines the use of atomic hydrogen to lessen the recombination current density in the borondoped region of n-type silicon solar cells. This required the development of a boron diffusion process that maintained the bulk lifetime of n-type silicon such that the recombination current density could be extracted by photoconductance spectroscopy. It is demonstrated that by hydrogenating boron diffusions, the majority carrier concentration can be controlled. By using symmetrically diffused test structures with quinhydrone-methanol surface passivation the recombination current density of a hydrogenated boron profile is shown to be less than that of a standard boron profile, by as much as 30%. This is then applied to a modified industrial silicon solar cell process to demonstrate an efficiency enhancement of 0.4%.

Full Text Available The effects of borondoping on the microstructural evolution and mechanical and electrical properties of age-hardenable Cu–4Ti (at.% alloys are investigated. In the quenched Cu–4Ti–0.03B (at.% alloy, elemental B (boron is preferentially segregated at the grain boundaries of the supersaturated solid-solution phase. The aging behavior of the B-doped alloy is mostly similar to that of conventional age-hardenable Cu–Ti alloys. In the early stage of aging at 450 °C, metastable β′-Cu4Ti with fine needle-shaped precipitates continuously form in the matrix phase. Cellular discontinuous precipitates composed of the stable β-Cu4Ti and solid-solution laminates are then formed and grown at the grain boundaries. However, the volume fraction of the discontinuous precipitates is lower in the Cu–4Ti–0.03B alloy than the Cu–4Ti alloy, particularly in the over-aging period of 72–120 h. The suppression of the formation of discontinuous precipitates eventually results in improvement of the hardness and tensile strength. It should be noted that minor B doping of Cu–Ti alloys also effectively enhances the elongation to fracture, which should be attributed to segregation of B at the grain boundaries.

This thesis is concerned with the characterisation of CVD diamond via spectroscopic and electrical investigations. Much of the work concentrates on the identification and the effects of defects and impurities. The bulk of the experimental results are from photoconductivity studies of CVD diamond configured as a detector of ultraviolet light. Other investigations include the annealing of radiation damage in CVD diamond and an electrical characterisation of boron-doped CVD diamond. The characterisation of some group III nitrides forms the short appendix. The work is organised into chapters which are outlined below. Chapter 1 - Introduction: This gives some background to the properties of diamond, its uses, and the different synthesis techniques. Also given is a short review of some of the optical centres in natural and CVD diamond. The kinetics of migration, which is relevant to later chapters is also discussed. Chapter 2 - Experimental Details: This chapter details the experimental techniques and apparatus used in all investigations. An outline of the electronics and data acquisition technique is also presented. Chapter 3 - The Annealing of Radiation Damage: This gives the annealing behaviour of some absorption features in natural and CVD diamond which has been irradiated with electrons. A correlation has been made between the annealing behaviour of two optical centres, and the fast and slow components of a vacancy related centre are explained. Chapter 4 - Electrical characterisation of boron-doped CVD diamond: The boron-dopeddiamonds studied in this chapter were intended for use as a detector of neutrons. This required a concentration of boron which is large enough for the detection process to occur but low enough for the 'leakage' current to not dominate any induced signal. This electrical characterisation measures the resistivities ( and the temperature dependence ) of the samples and compares this to other work to estimate boron concentrations. Chapter 5 - CVD

The electrochemical oxidation of chloranilic acid (CAA) has been studied in acidic media at Pb/PbO 2 , boron-dopeddiamond (Si/BDD) and Ti/IrO 2 electrodes by bulk electrolysis experiments under galvanostatic control. The obtained results have clearly shown that the electrode material is an important parameter for the optimization of such processes, deciding of their mechanism and of the oxidation products. It has been observed that the oxidation of CAA generates several intermediates eventually leading to its complete mineralization. Different current efficiencies were obtained at Pb/PbO 2 and BDD, depending on the applied current density in the range from 6.3 to 50 mA cm -2 . Also the effect of the temperature on Pb/PbO 2 and BDD electrodes was studied. UV spectrometric measurements were carried out at all anodic materials, with applied current density of 25 and 50 mA cm -2 . These results showed a faster CAA elimination at the BDD electrode. Finally, a mechanism for the electrochemical oxidation of CAA has been proposed according to the results obtained with the HPLC technique

For the future, one of the biggest challenge faced to the technologies of flat panel display and various optoelectronic and photovoltaic devices is to find an alternative to the use of transparent conducting oxides like ITO. In this new approach, the objective is to grow high conductive thin-layer graphene (TLG) on the top of diamond-like carbon (DLC) layers presenting high performance. DLC prepared by pulsed laser deposition (PLD) have attracted special interest due to a unique combination of their properties, close to those of monocrystalline diamond, like its transparency, hardness and chemical inertia, very low roughness, hydrogen-free and thus high thermal stability up to 1000 K. In our future work, we plane to explore the synthesis of conductive TLG on top of insulating DLC thin films. The feasibility and obtained performances of the multi-layered structure will be explored in great details in the short future to develop an alternative to ITO with comparable performance (conductivity of transparency). To select the best DLC candidate for this purpose, we focus this work on the physicochemical properties of the DLC thin films deposited by PLD from a pure graphite target at two wavelengths (193 and 248 nm) at various laser fluences. A surface graphenization process, as well as the required efficiency of the complete structure (TLG/DLC) will clearly be related to the DLC properties, especially to the initial sp3/sp2 hybridization ratio. Thus, an exhaustive description of the physicochemical properties of the DLC layers is a fundamental step in the research of comparable performance to ITO.

Aluminum-doped diamond samples were synthesized using the conventional microwave plasma chemical vapor deposition method. The electronic structures were measured using an electron probe microanalyzer and by X-ray photoelectron spectroscopy. The area intensity of the partial profile of Al-3p near the Fermi level increased with increasing aluminum concentration in the sample. The partial profile of Al-3p resembles that of C-2p at high aluminum concentrations, which suggests strong hybridization between Al-3p and C-2p. Additionally, the temperature dependence of the electric resistance yields an activation energy of 8.2 meV at room temperature. The present results suggest the metal-insulator transition of aluminum-doped diamond, similar to that of boron-dopeddiamond. However, with increasing aluminum concentration, a considerable amount of carriers is not doped to C-2p orbitals in aluminum-doped diamond. The present results indicate that superconductivity in aluminum-doped diamond with the same mechanism as that in boron-dopeddiamond does not occur.

Semiconductor diamond is considered the best heater material to generate ultra-high temperatures in a Kawai cell. In two pioneering studies, a mixture of graphite and amorphous boron (or boron carbide, B4C) was converted to semiconductor diamond in the diamond stability field and was confirmed to generate 2000°C and 3500°C, respectively. Following these works, we synthesized a homemade boron-doped graphite block with fine machinability. With this technical breakthrough, we developed a semiconductor diamond heater in a smaller Kawai-type cell assembly. Here, we report the procedure for making machinable boron-doped graphite, and the performance of the material as a heater in a Kawai cell at 15 GPa using tungsten carbide anvils and at ∼50 GPa using sintered diamond anvils. Furthermore, we present a finite element simulation of the temperature distribution generated by a semiconductor diamond heater, which is much more homogeneous than that generated by a metal heater.

Electrochemical oxidation of Basic Red 29 (BR29) was studied in a bipolar trickle tower (BTT) reactor by using Raschig ring shaped boron-dopeddiamond (BDD) electrodes, which were originally employed by the present researchers, in a recirculated batch mode. The model solution was prepared with BR29 using distilled water. The effects of initial dye concentration, Na 2 SO 4 concentration as supporting electrolyte, current density, flow rate and initial pH on the removal efficiency were investigated, and practically, complete BR29 removal (over 99%) was obtained in all the studies. After optimum experimental conditions were determined, textile wastewater has also studied by monitoring the destruction of color and COD. With the textile wastewater, 97.2% of color and 91% of COD removal were, respectively, achieved at the current density of 1 mA/cm 2 . Microtox toxicity tests were performed in both BR29 solution and textile wastewater under optimum experimental conditions, and relatively good toxicity reductions were obtained with respect to the initial values. According to the results, BDD anode was seen to be a unique material for the degradation of BR29 and COD and also the reduction of toxicity simultaneously

Thin film diamond is of particular interest because of its wide applicability, including its potential use in high temperature electronics. This thesis describes a study of some of the processing stages required to exploit thin film diamond as an electronic device. Initial experiments were carried out to optimise bi-metallic contact schemes on orientated diamond film using electrical measurements and chemical analysis. Temperature stability was also investigated and it was concluded that the most favourable ohmic contact scheme is aluminium-on-titanium. Further electrical measurements confirmed that the contribution of resistance made by the contacts themselves to the metal/diamond/metal system overall was acceptably low, specifically 6 Ω.cm 2 for an undoped diamond system and less than 3 x 10 -6 Ω.cm 2 for borondopeddiamond. To improve the as-grown resistivity of diamond films, an oxygen/argon plasma etch process was applied. The input parameters of the plasma system were optimised to give the maximum achievable resistivity of 4 x 10 11 Ω.cm. This was attained using a statistical design procedure via analysis of resistivity and etch rate outputs. Having optimised post growth treatment and contact metallisation, undoped and doped orientated diamond films were characterised via voltage and temperature dependencies. It was concluded that the dominant charge transport mechanisms for undoped diamond, nitrogen and borondopeddiamond were variable range hopping at low temperatures up to 523 K and grain boundary effects. At higher temperatures, valence or impurity band conduction appeared to be the probable mechanisms with activation energies of 0.23 eV for nitrogen doped diamond and 0.08 eV for borondopeddiamond. Preliminary experiments electrical properties of diamond and initial results suggested the presence of a high density of recombination centres. The final stage of experimental research initiated a study of direct electron beam writing lithography to

Full Text Available This work reported new voltammetric/amperometric-based protocols using a commercial boron-dopeddiamond (BDD electrode for simple and fast simultaneous detection of sulfide and nitrite from water. Square-wave voltammetry operated under the optimized working conditions of 0.01 V step potential, 0.5 V modulation amplitude and 10 Hz frequency allowed achieving the best electroanalytical parameters for the simultaneous detection of nitrite and sulfide. For practical in-field detection applications, the multiple-pulsed amperometry technique was operated under optimized conditions, i.e., −0.5 V/SCE for a duration of 0.3 s as conditioning step, +0.85 V/SCE for a duration of 3 s that assure the sulfide oxidation and +1.25 V/SCE for a duration of 0.3 s, where the nitrite oxidation occurred, which allowed the simultaneously detection of sulfide and nitrite without interference between them. Good accuracy was found for this protocol in comparison with standardized methods for each anion. Also, no interference effect was found for the cation and anion species, which are common in the water matrix.

Full Text Available The purpose of the present paper is to give an overview on the current development status of nanocrystalline diamondelectrodes for electrochemical applications. Firstly, we describe a brief comparison between the general properties of nanocrystalline diamond (undoped and boron-doped and boron-doped microcrystalline diamond films. This is followed by a summary of the nanodiamond preparation methods. Finally, we present a discussion about the undoped and boron-doped nanocrystalline diamond and their characteristics, electrochemical properties, and practical applications.

Recently topological materials have attracted much attention due to their quantization transports as well as edge states. It will be excellent to realize the robust quantum anomalous Hall transports in graphene-based devices. Using density-functional theory and tight-binding method, we investigated the structural, magnetic and topological properties for the boron-doped graphene with Re-adsorption. A large band-gap of 32.5 meV is opened by the Rashba spin-orbital coupling, and the band-gap is robust against the shape deformation of ± 4% along the zigzag direction. Giant magnetic anisotropy emerges in this adsorption system together with the Fermi level lying in the band gap. Both the magnetic anisotropy and the band gap can be tuned by a moderate electric field. Calculations reveal that the system exhibits the quantization transports with the Chern number C=2 .

This work presents a study on degradation of indigo carmine dye in a filter-press type FM01-LC reactor using Sb2O5-doped Ti/IrO2-SnO2 dimensionally stable anode (DSA) electrodes. Micro- and macroelectrolysis studies were carried out using solutions of 0.8 mM indigo carmine in 0.05 M NaCl, which resemble blue denim laundry industrial wastewater. Microelectrolysis results show the behaviour of DSA electrodes in comparison with the behaviour of boron-dopeddiamond (BDD) electrodes. In general, dye degradation reactions are carried out indirectly through active chlorine generated on DSA, whereas in the case of BDD electrodes more oxidizing species are formed, mainly OH radicals, on the electrode surface. The well-characterized geometry, flow pattern and mass transport of the FM01-LC reactor used in macroelectrolysis experiments allowed the evaluation of the effect of hydrodynamic conditions on the chlorine-mediated degradation rate. Four values of Reynolds number (Re) (93, 371, 464 and 557) at four current densities (50, 100, 150 and 200 A/m2) were tested. The results show that the degradation rate is independent of Re at low current density (50 A/m2) but becomes dependent on the Re at high current density (200 A/m2). This behaviour shows the central role of mass transport and the reactor parameters and design. The low energy consumption (2.02 and 9.04 kWh/m3 for complete discolouration and chemical oxygen demand elimination at 50 A/m2, respectively) and the low cost of DSA electrodes compared to BDD make DSA electrodes promising for practical application in treating industrial textile effluents. In the present study, chlorinated organic compounds were not detected.

Nanocrystalline diamond- (NCD) and AlN-based ultrathin single layer and bilayer membranes are investigated towards their mechanical properties. It is shown that chemo-mechanical polishing and heavy borondoping of NCD thin films do not impact the elastic properties of NCD layers as revealed by negligible variations of the NCD Young's modulus (E). In addition, it is demonstrated that the combination of NCD elastic layer and AlN piezo-actuator is highly suitable for the fabrication of mechanically stable ultrathin membranes in comparison to AlN single layer membranes. The elastic parameters of NCD/AlN heterostructures are mainly determined by the outstanding high Young's modulus of NCD (E = 1019 ± 19 GPa). Such ultrathin unimorph membranes allow for fabrication of piezo-actuated AlN/NCD microlenses with tunable focus length. - Highlights: • Mechanical properties of nanocrystalline diamond (NCD) and AlN circular membranes • No influence of polishing of NCD thin films on the mechanical properties of NCD • No influence of heavy boron-doping on the mechanical properties of NCD • Demonstration of mechanically stable piezo-actuated NCD/AlN membranes • Reported performance of AlN/NCD microlenses with adjustable focus length.

Highlights: •More defective sites in graphene after the doping of boron atoms. •Fine dispersion of Pt nanoparticles supported on boron-doped graphene. •Low electron transfer resistance at boron-doped graphene. •High performance of boron-doped graphene as an electrode material or a support for Pt catalysts. -- Abstract: Boron-doped graphene (BGR) is prepared by thermal annealing of graphene oxide (GO) in the presence of boric acid. More defective sites are introduced into GR accompanied by the doping of boron. Low electron transfer resistance towards redox probe is observed at BGR. The BGR modified electrode can effectively distinguish the anodic peaks for ascorbic acid (AA), dopamine (DA), and uric acid (UA). The defective sites of BGR can also act as anchoring sites for the deposition of Pt nanoparticles. When used as a support for Pt electrocatalysts, Pt nanoparticles with an average diameter of 3.2 nm are deposited on BGR. The doping of boron into GR facilitates the dispersion of Pt nanoparticles and increases the utilization efficiency of Pt nanoparticles. The Pt/BGR exhibits significant catalytic activity towards the oxidation of methanol. The results demonstrate that BGR is a good support for Pt catalysts or an electrode material compared with the undoped GR

Diamond is considered as an ideal material for high field and high power devices due to its high breakdown field, high lightly doped carrier mobility, and high thermal conductivity. The modeling and simulation of diamond devices are therefore important to predict the performances of diamond based devices. In this context, we use Silvaco ® Atlas, a drift-diffusion based commercial software, to model diamond based power devices. The models used in Atlas were modified to account for both variable range and nearest neighbor hopping transport in the impurity bands associated with high activation energies for borondoped and phosphorus doped diamond. The models were fit to experimentally reported resistivity data over a wide range of doping concentrations and temperatures. We compare to recent data on depleted diamond Schottky PIN diodes demonstrating low turn-on voltages and high reverse breakdown voltages, which could be useful for high power rectifying applications due to the low turn-on voltage enabling high forward current densities. Three dimensional simulations of the depleted Schottky PIN diamond devices were performed and the results are verified with experimental data at different operating temperatures

Diamond is considered as an ideal material for high field and high power devices due to its high breakdown field, high lightly doped carrier mobility, and high thermal conductivity. The modeling and simulation of diamond devices are therefore important to predict the performances of diamond based devices. In this context, we use Silvaco® Atlas, a drift-diffusion based commercial software, to model diamond based power devices. The models used in Atlas were modified to account for both variable range and nearest neighbor hopping transport in the impurity bands associated with high activation energies for borondoped and phosphorus doped diamond. The models were fit to experimentally reported resistivity data over a wide range of doping concentrations and temperatures. We compare to recent data on depleted diamond Schottky PIN diodes demonstrating low turn-on voltages and high reverse breakdown voltages, which could be useful for high power rectifying applications due to the low turn-on voltage enabling high forward current densities. Three dimensional simulations of the depleted Schottky PIN diamond devices were performed and the results are verified with experimental data at different operating temperatures

Diamond is considered as an ideal material for high field and high power devices due to its high breakdown field, high lightly doped carrier mobility, and high thermal conductivity. The modeling and simulation of diamond devices are therefore important to predict the performances of diamond based devices. In this context, we use Silvaco{sup ®} Atlas, a drift-diffusion based commercial software, to model diamond based power devices. The models used in Atlas were modified to account for both variable range and nearest neighbor hopping transport in the impurity bands associated with high activation energies for borondoped and phosphorus doped diamond. The models were fit to experimentally reported resistivity data over a wide range of doping concentrations and temperatures. We compare to recent data on depleted diamond Schottky PIN diodes demonstrating low turn-on voltages and high reverse breakdown voltages, which could be useful for high power rectifying applications due to the low turn-on voltage enabling high forward current densities. Three dimensional simulations of the depleted Schottky PIN diamond devices were performed and the results are verified with experimental data at different operating temperatures.

Tetrahedral amorphous carbon (ta-C) consists of a mixture of sp(3)- and sp(2)-bonded carbon ranging from 60 to 40% (sp(3)/sp(3)+sp(2)) depending on the deposition conditions. The physical, chemical, and electrochemical properties depend on the sp(2)/sp(3) bonding ratio as well as the presence of incorporated impurities, such as hydrogen or nitrogen. The ability to grow ta-C at lower temperatures (25-100 °C) on a wider variety of substrates as compared to CVD diamond is an advantage of this material. Herein, we report on the structural and electrochemical properties of nitrogen-incorporated ta-C thin films (ta-C:N). The incorporation of nitrogen into the films decreases the electrical resistivity from 613 ± 60 (0 sccm N(2)) to 1.10 ± 0.07 Ω-cm (50 sccm N(2)), presumably by increasing the sp(2)-bonded carbon content and the connectedness of these domains. Similar to boron-dopeddiamond, these materials are characterized by a low background voltammetric current, a wide working potential window (~ 3 V), and relatively rapid electron-transfer kinetics for aqueous redox systems, including Fe(CN)(6)(-3/-4) and Ru(NH(3))(6)(+3/+2), without conventional pretreatment. Additionally, there is weak molecular adsorption of polar molecules (methylene blue) on the ta-C surface. Overall, the properties of the ta-C and ta-C:N electrodes are such that they could be excellent new choices for electroanalytical measurements.

In present work, the two-step anodization technique was applied for synthesis of TiO2 nanotube (NT). Silver and diamond like carbon (DLC) were coated on the surface of as prepared TiO2-NT using chemical reduction method and MW ECR plasma system. The morphology, composition and structure of the electrodes were examined by field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray spectroscopy (EDX) and X-ray diffraction (XRD). The results showed that Ag nanoparticles, having size in the range of 48-115 nm, are evenly distributed on the top, inside and outside surface of TiO2-NT and when DLC was coated on the surface of TiO2-NT and TiO2-NT-Ag, the top of nanotubes were partially open and the pore diameter of hexagonal structure decreased from 165 nm to of 38-80 nm. On the other hand, the microhardness test and contact angle measurements revealed that additions of Ag and diamond like carbon have a positive effect on the mechanical properties of TiO2-NT film. The electrocatalytic properties of the electrodes towards the hydrogen evolution reaction (HER) were investigated by the electrochemical measurements recorded in 1 M KOH solution. In addition, long-term durability of electrodes towards HER and the energy consumption of alkaline electrolysis were investigated. The energy requirement showed that while the deposition of silver provides approximately 14.95% savings of the energy consumption, the DLC coating causes increase in energy consumption.

The modification of the steep and sharp valleys on the surface of the boron-doped zinc oxide (BZO) front electrodes by plasma surface treatment is a critical process for avoiding a significant reduction in the electrical performance of thin-film silicon solar cells. In this work, we report the origin of the changes in the electrical and optical properties of the BZO films that occur after this process. On the basis of an analysis of the chemical states, we found an improvement of the carrier concentration along with the treatment time that was mainly due to an increase of the oxygen vacancy. This indicated a deficiency of the oxygen in the BZO films under argon-ion bombardment. The red-shift of the A1 longitudinal optical mode frequency in the Raman spectra that was attributed to the existence of vacancy point defects within the films also strengthened this argument. The significant reduction of the haze ratio as well as the appearance of interference peaks on the transmittance spectra as the treatment time was increased were mainly due to the smoothing of the film surface, which indicated a degradation of the light-scattering capability of the BZO films. We also observed a gain of the visible-region transmittance that was attributed to the decrease of the thickness of the BZO films after the plasma surface treatment, instead of the crystallinity improvement. On the basis of our findings, we have proposed a further design rule of the BZO front electrodes for thin-film silicon solar cell applications.

Electrocatalytic, switchable hydrogen storage promises both tunable kinetics and facile reversibility without the need for specific catalysts. The feasibility of this approach relies on having materials that are easy to synthesize, possessing good electrical conductivities. Graphitic carbon nitride (g-C 4 N 3 ) has been predicted to display charge-responsive binding with molecular hydrogen-the only such conductive sorbent material that has been discovered to date. As yet, however, this conductive variant of graphitic carbon nitride is not readily synthesized by scalable methods. Here, we examine the possibility of conductive and easily synthesized boron-doped graphene nanosheets (B-doped graphene) as sorbent materials for practical applications of electrocatalytically switchable hydrogen storage. Using first-principle calculations, we find that the adsorption energy of H 2 molecules on B-doped graphene can be dramatically enhanced by removing electrons from and thereby positively charging the adsorbent. Thus, by controlling charge injected or depleted from the adsorbent, one can effectively tune the storage/release processes which occur spontaneously without any energy barriers. At full hydrogen coverage, the positively charged BC 5 achieves high storage capacities up to 5.3 wt %. Importantly, B-doped graphene, such as BC 49 , BC 7 , and BC 5 , have good electrical conductivity and can be easily synthesized by scalable methods, which positions this class of material as a very good candidate for charge injection/release. These predictions pave the route for practical implementation of electrocatalytic systems with switchable storage/release capacities that offer high capacity for hydrogen storage.

Borondoped bcc-W (WBx, x = B/W) films were deposited on Si(100) substrates by magnetron co-sputtering pure W and B targets. Our results reveal that when the absolute value of substrate bias voltage (Vb) increases from floating to 240 V, the value of x monotonously decreases from 0.18 to 0.04, accompanied by a phase transition from a mixture of tetragonal γ-W2B and body-centered cubic α-W(B) phase (-Vb ≤ 60 V) to α-W(B) single phase (-Vb > 60 V). Hardness, depending on Vb, increases first and then drops, where the maximum hardness of 30.8 GPa was obtained at -Vb = 60 V and far higher than pure W and W2B theoretical value. In the mixed phase structure, the grain boundaries strengthening, Hall-Petch effect and solid-solution strengthening induced by B dominate the strengthening mechanism. Astonishingly, the film grown at -Vb = 120 V still possesses twice higher hardness than pure W, wherein unexpectedly low (6.7 at.%) B concentration and only the single α-W(B) phase can be identified. In this case, both Hall-Petch effect and solid-solution strengthening work. Besides, low friction coefficient of ∼0.18 can be obtained for the films with α-W(B) phase, which is competitive to that of reported B-rich transition-metal borides, such as TiB2, CrB and CrB2.

The doped boron (B) atom in silicon carbide nanotube (SiCNT) can substitute carbon or silicon atom, forming two different structures. The transport properties of both B-doped SiCNT structures are investigated by the method combined non-equilibrium Green's function with density functional theory (DFT). As the bias ranging from 0.8 to 1.0 V, the negative differential resistance (NDR) effect occurs, which is derived from the great difficulty for electrons tunneling from one electrode to another with the increasing of localization of molecular orbital. The high similar transport properties of both B-doped SiCNT indicate that boron is a suitable impurity for fabricating nano-scale SiCNT electronic devices.

A small-sized generator of ozonated water was developed using an electro-conductive diamond. We studied the optimum conditions for producing ozonated water. As a result, we developed a small-sized generator of ozonated water driven by a dry-cell for use in the average household. This generator was easily able to produce ozonated water with an ozone concentration (over 4 mg/L) sufficient for disinfection. In addition, we verified the high disinfecting performance of the water produced in an actual hospital.

Highlights: ► We investigate the properties of phosphorus and boron-doped silicon nitride films. ► Phosphorus-doped layers yield higher lifetimes than undoped ones. ► The fixed charges density decreases when increasing the films phosphorus content. ► Boron-doped films feature very low lifetimes. ► These doped layers are of particular interest for crystalline silicon solar cells. -- Abstract: Dielectric layers are of major importance in crystalline silicon solar cells processing, especially as anti-reflection coatings and for surface passivation purposes. In this paper we investigate the fixed charge densities (Q{sub fix}) and the effective lifetimes (τ{sub eff}) of phosphorus (P) and boron (B) doped silicon nitride layers deposited by plasma-enhanced chemical vapour deposition. P-doped layers exhibit a higher τ{sub eff} than standard undoped layers. In contrast, B-doped layers exhibit lower τ{sub eff}. A strong Q{sub fix} decrease is to be seen when increasing the P content within the film. Based on numerical simulations we also demonstrate that the passivation obtained with P- and B-doped layers are limited by the interface states rather than by the fixed charges.

Un-doped and carbon or/and borondoped Cadmium sulfide nanoparticles were prepared via chemical co-precipitation procedure by Polyvinyl pyrrolidone (PVP) as a stabilizer. The optical and structural properties were investigated using several techniques. The morphology of CdS nanophotocatalyst was characterized using X-ray diffraction (XRD) and scanning electron microscopy. The optical properties of both un-doped and doped samples were carried out by photoluminescence (PL) spectroscopy and UV–vis Diffuse reflectance spectra (DRS). An optimum doping level of the atoms dopant for enhanced PL properties are found through optical study. Degradation of Amoxicillin under UV light elucidation was applied to appraise the photocatalytic efficiency. The results show that the carbon and borondoping CdS nanoparticles has high potential in green chemistry. - Highlights: • Un-doped, C or/and B-doped CdS nanoparticles were successfully synthesized. • The Blue shift was observed in UV–vis absorption spectra for the doped nanoparticles. • Doping of CdS with C and B enhances the fluorescence

Un-doped and carbon or/and borondoped Cadmium sulfide nanoparticles were prepared via chemical co-precipitation procedure by Polyvinyl pyrrolidone (PVP) as a stabilizer. The optical and structural properties were investigated using several techniques. The morphology of CdS nanophotocatalyst was characterized using X-ray diffraction (XRD) and scanning electron microscopy. The optical properties of both un-doped and doped samples were carried out by photoluminescence (PL) spectroscopy and UV–vis Diffuse reflectance spectra (DRS). An optimum doping level of the atoms dopant for enhanced PL properties are found through optical study. Degradation of Amoxicillin under UV light elucidation was applied to appraise the photocatalytic efficiency. The results show that the carbon and borondoping CdS nanoparticles has high potential in green chemistry. - Highlights: • Un-doped, C or/and B-doped CdS nanoparticles were successfully synthesized. • The Blue shift was observed in UV–vis absorption spectra for the doped nanoparticles. • Doping of CdS with C and B enhances the fluorescence.

In the ideal form diamond displays extreme physical, optical and electronic properties, making this material interesting for many device applications. However, natural or high pressure, high temperature synthesised forms of diamond are not useful since they are only available as small irregular crystallites and are expensive. The emergence of commercially accessible techniques for the formation of thin films of diamond over relatively large areas has changed this situation, enabling the prospects for the use of diamond as an electronic material to be truly evaluated. Thin film diamond is a defective polycrystalline material. It is difficult to dope n- and p-type and resists conventional chemical etching. Thus, despite the superlative properties of ideal diamond, the realisation of useful devices from this material is far from simple. This thesis considers how the problems may be overcome such that high performance diamond devices can be realised for use in high temperature, high power and high radiation environments. Following a review of the current state-of-the-art in diamond device technology the experimental techniques used throughout this study are summarised. Field effect transistors (FETs) have been designed for operation at high (>300 deg. C) temperatures. Boron-doped (p-type) diamond was used to form the active channel, with insulating diamond acting as the gate to the FET structure. Polycrystalline diamond devices with the highest yet reported transconductance values, which display full turn-off characteristics have been produced. To enable room temperature operation, where boron is an ineffective dopant, a novel doping approach has been established using hydrogen; devices with transconductance, power handling and full pinch-off characteristic have been realised for the first time with this approach. More complex devices require patterning of the diamond substrate material; reactive ion etching using oxygen and chlorinated fluorocarbons have been studied

CVD diamond nucleation is investigated using the hot filament technique. The stability of CVD diamond at elevated temperatures in vacuum, O_2, and atomic hydrogen environments are studied using photoemission electron microscopy (PEEM) combined with in-vacuo x-ray photoelectron spectroscopy (XPS). Dissolution, oxidation, and atomic hydrogen etching processes of CVD diamond are observed in real-time. Low field cold electron emission from CVD diamond films has been observed for the first time by PEEM. Nucleation density Mo substrates could be increased from 10^4 to rm 10 ^8/cm^2 by polishing. Heating the substrate to 870^circC in vacuum prior to deposition, or above 1000^ circC at the beginning of deposition, reduced nucleation by more than 100-fold. Reduction in nucleation sites is attributed to annealing. Nucleation on Mo _2C substrates was found to be very poor rm (10^4/cm^2), which shows carbide alone does not promote nucleation. Carbide formation may remove nucleation sites. CVD diamond was found to dissolve into the Mo substrate in vacuum at about 1200^circ C. XPS showed formation of Mo_2 C when the diamond dissolved. Diamond oxidation to gas phase products occurred directly at about 600 ^circC, with no observable participation by the substrate. No detectable etching by atomic hydrogen at a pressure of 1times10^{-4 } torr was observed. Borondoped and "pure" CVD diamond films were found to emit electrons at room temperature under the action of the accelerating electric field of the PEEM (about 30 kV/cm) without photon excitation. The mechanism underlying this phenomenon was investigated with PEEM and by studying the emission current-vs-voltage characteristics of the CVD diamond films. Morphology and crystalline orientation were found to play only a minor role. Impurities in the CVD diamond structure lowers the potential barrier substantially; tunneling of electrons into the vacuum is facile. The effective work function of the emitting CVD diamond films is

Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-dopeddiamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na{sub 2}SO{sub 4}. The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test.

Despite many works are devoted to oxidation of diamond surfaces, it is still a challenge, to successfully produce well defined 'C-O' functions, particularly for functionalization purposes. In this paper we describe and compare, for the first time, the 'electroless' oxidation of as-deposited polycrystalline boron-dopeddiamond (BDD) films in ceric and ferricyanide solutions at room temperature. Both reactions efficiently generate oxygen functionalities on BDD surface. While a higher amount of 'C-O' moieties is produced with Ce{sup 4+} as oxidizing agent, the use of ferricyanide specie seems the most interesting to specifically generate hydroxyl groups. Additionally, this easy to perform oxidative method appears not damaging for diamond surfaces and adapted to conductive or non-conductive materials. The resulting surfaces were characterized using X-ray photoelectron spectroscopy, contact angle and capacitance-voltage analysis.

In an Accelerator-based neutron irradiation field using 7 Li(p, n) 7 Be neutrons by 1.95 MeV protons, the distributions of 10 B reaction rates and thermal neutron fluence in a water phantom were measured using Boron-doped CR-39 and Au activation analysis, respectively. Comparing the results of the measurements, we discussed the validity of the evaluation method of 10 B reaction rate using thermal neutron fluence. (author)

In this paper, interactions of carbon monoxide (CO) and hydrogen sulfide (H2S) with doped and decorated graphene were investigated by using density functional theory and quantum-espresso packages. First of all, impurity effects and properties like adsorption mechanism, the more probable position, binding energy, bond length, Lowdin charge analyze and density of state (DOS) have been determined and then the properties of CO and H2S adsorption calculated, and a brief comparison with other studies has been done. All of these lead to tuning the electronic structure of graphene sheet with impurities that show higher affinities with H2S and CO molecules in comparison to pristine graphene. The obtained results from DOS and charge transfer show that electrical conductance of the B doped graphene sheet and CuO Nano particle decorated—Borondoped graphene sheets are significantly changed compared to the pristine graphene sheet by an increase in the electronic states of near the Fermi’s energy states.

We study hole transport properties in physically defined p-type silicon quantum dots (QDs) on a heavily doped silicon-on-insulator (SOI) substrate. We observe Coulomb diamonds using single QDs and estimate the charging energy as ∼1.6 meV. We obtain the charge stability diagram of double QDs using single QDs as a charge sensor. This is the first demonstration of charge sensing in p-type heavily doped silicon QDs. For future time-resolved measurements, we apply radio-frequency reflectometry using impedance matching of LC circuits to the device. We observe the resonance and estimate the capacitance as ∼0.12 pF from the resonant frequency. This value is smaller than that of the devices with top gates on nondoped SOI substrate. This indicates that high-frequency signals can be applied efficiently to p-type silicon QDs without top gates.

Full Text Available In a recent X-ray absorption study in borondopeddiamond, Nakamura et al. have seen a well isolated narrow boron impurity band in non-superconducting samples and an additional narrow band at the chemical potential in a superconducting sample. We interpret the beautiful spectra as evidence for upper Hubbard band of a Mott insulating impurity band and an additional metallic 'mid-gap band' of a conducting 'self-doped' Mott insulator. This supports the basic framework of a recent theory of the present author of strongly correlated impurity band superconductivity (impurity band resonating valence bond, IBRVB theory in a template of a wide-gap insulator, with no direct involvement of valence band states.

By using different deposition conditions, the CVD diamond films with different qualities and orientation were grown by the hot-filament CVD technique. The object of this article is to summarize and discuss relation between structural, physical and electrochemical properties of different diamondelectrodes. The physical properties of the Hot Filament CVD microcrystalline diamond films are analyzed by scanning electron microscopy and Raman spectroscopy. In presented studies two different electrodes were used of the diamond grain sizes around 200 nm and 10 μm, as it was estimated from SEM picture. The diamond layers quality was checked on basis of FWHM (Full width at Half Maximum) of 1332 cm −1 diamond Raman peak. The ratio of sp 3 /sp 2 carbon bonds was determined by 1550 cm −1 G band and 1350 cm −1 D band in the Raman spectrum. The electrochemical properties were analyzed using (CV) cyclic voltammetry measurements in aqueous solutions. The sensitivity of undoped diamondelectrodes depends strongly on diamond film quality and concentration of amorphous carbon phase in the diamond layer

Diamond exhibits several special properties, for example good biocompatibility and a large electrochemical potential window, that make it particularly suitable for biofunctionalization and biosensing. Here we show that proteins can be attached covalently to nanocrystalline diamond thin films. Moreover, we show that, although the biomolecules are immobilized at the surface, they are still fully functional and active. Hydrogen-terminated nanocrystalline diamond films were modified by using a photochemical process to generate a surface layer of amino groups, to which proteins were covalently attached. We used green fluorescent protein to reveal the successful coupling directly. After functionalization of nanocrystalline diamondelectrodes with the enzyme catalase, a direct electron transfer between the enzyme's redox centre and the diamondelectrode was detected. Moreover, the modified electrode was found to be sensitive to hydrogen peroxide. Because of its dual role as a substrate for biofunctionalization and as an electrode, nanocrystalline diamond is a very promising candidate for future biosensor applications.

The objective of this research proposal was to address the separation and sequestration of Kr and I from each other using nano-sized diamond particles and retaining these in diamond until they decay to the background level or can be used as a byproduct. Following removal of Kr and I, an adsorbent will be used to adsorb and store CO2 from the CO2 rich stream. A Field Enhanced Diffusion with Optical Activation (FEDOA-a large scale process that takes advantage of thermal, electrical, and optical activation to enhance the diffusion of an element into diamond structure) was used to load Kr and I on micron or nano sized particles having a larger relative surface area. The diamond particles can be further increased by doping it with boron followed by irradiation in a neutron flux. Previous studies showed that the hydrogen storage capacity could be increased significantly by using boron-doped irradiated diamond particles. Diamond powders were irradiated for a longer time by placing them in a quartz tube. The surface area was measured using a Quantachrome Autosorb system. No significant increase in the surface area was observed. Total surface area was about 1.7 m2/g. This suggests the existence of very minimal pores. Interestingly it showed hysteresis upon desorption. A reason for this may be strong interaction between the surface and the nitrogen molecules. Adsorption runs at higher temperatures did not show any adsorption of krypton on diamond. Use of a GC with HID detector to determine the adsorption capacity from the breakthrough curves was attempted, but experimental difficulties were encountered.

Over the last decades, carbon-based nanostructures have generated a huge interest from both fundamental and technological viewpoints owing to their physicochemical characteristics, markedly different from their corresponding bulk states. Among these nanostructured materials, carbon nanotubes (CNTs), and more recently graphene and its derivatives, hold a central position. The large amount of work devoted to these materials is driven not only by their unique mechanical and electrical properties, but also by the advances made in synthetic methods to produce these materials in large quantities with reasonably controllable morphologies. While much less studied than CNTs and graphene, diamond nanowires, the diamond analogue of CNTs, hold promise for several important applications. Diamond nanowires display several advantages such as chemical inertness, high mechanical strength, high thermal and electrical conductivity, together with proven biocompatibility and existence of various strategies to functionalize their surface. The unique physicochemical properties of diamond nanowires have generated wide interest for their use as fillers in nanocomposites, as light detectors and emitters, as substrates for nanoelectronic devices, as tips for scanning probe microscopy as well as for sensing applications. In the past few years, studies on boron-dopeddiamond nanowires (BDD NWs) focused on increasing their electrochemical active surface area to achieve higher sensitivity and selectivity compared to planar diamond interfaces. The first part of the present review article will cover the promising applications of BDD NWS for label-free sensing. Then, the potential use of diamond nanowires as inorganic substrates for matrix-free laser desorption/ionization mass spectrometry, a powerful label-free approach for quantification and identification of small compounds, will be discussed.

Full Text Available Over the last decades, carbon-based nanostructures have generated a huge interest from both fundamental and technological viewpoints owing to their physicochemical characteristics, markedly different from their corresponding bulk states. Among these nanostructured materials, carbon nanotubes (CNTs, and more recently graphene and its derivatives, hold a central position. The large amount of work devoted to these materials is driven not only by their unique mechanical and electrical properties, but also by the advances made in synthetic methods to produce these materials in large quantities with reasonably controllable morphologies. While much less studied than CNTs and graphene, diamond nanowires, the diamond analogue of CNTs, hold promise for several important applications. Diamond nanowires display several advantages such as chemical inertness, high mechanical strength, high thermal and electrical conductivity, together with proven biocompatibility and existence of various strategies to functionalize their surface. The unique physicochemical properties of diamond nanowires have generated wide interest for their use as fillers in nanocomposites, as light detectors and emitters, as substrates for nanoelectronic devices, as tips for scanning probe microscopy as well as for sensing applications. In the past few years, studies on boron-dopeddiamond nanowires (BDD NWs focused on increasing their electrochemical active surface area to achieve higher sensitivity and selectivity compared to planar diamond interfaces. The first part of the present review article will cover the promising applications of BDD NWS for label-free sensing. Then, the potential use of diamond nanowires as inorganic substrates for matrix-free laser desorption/ionization mass spectrometry, a powerful label-free approach for quantification and identification of small compounds, will be discussed.

Diamond is an especially attractive material because of its gemological value as well as its unique mechanical, chemical and physical properties. One of these properties is that boron-dopeddiamond is an electrically p-type semiconducting material at practically any boron concentration. This property makes it possible to use diamonds for multiple industrial and technological applications. Boron can be incorporated into pure diamond by different techniques including ion implantation. Although typical energies used to dope diamond by ion implantation are about 100 keV, implantations have also been performed with energies above MeV. In this work CMAM microbeam setup has been used to demonstrate capability to implant boron with high energies. An 8 MeV boron beam with a size of about 5 × 3 μm{sup 2} and a beam current higher than 500 pA has been employed while controlling the beam position and fluence at all irradiated areas. The subsequent mapping of the implanted boron in diamond has been obtained using the strong and broad nuclear reaction {sup 11}B(p, α){sup 8}Be at E{sub p} = 660 keV. This reaction has a high Q-value (8.59 MeV for α{sub 0} and 5.68 MeV for α{sub 1}) and thus is almost interference-free. The sensitivity of the technique is studied in this work.

Full Text Available We demonstrate the coupling of single color centers in diamond to plasmonic and dielectric photonic structures to realize novel nanophotonic devices. Nanometer spatial control in the creation of single color centers in diamond is achieved by implantation of nitrogen atoms through high-aspect-ratio channels in a mica mask. Enhanced broadband single-photon emission is demonstrated by coupling nitrogen–vacancy centers to plasmonic resonators, such as metallic nanoantennas. Improved photon-collection efficiency and directed emission is demonstrated by solid immersion lenses and micropillar cavities. Thereafter, the coupling of diamond nanocrystals to the guided modes of micropillar resonators is discussed along with experimental results. Finally, we present a gas-phase-doping approach to incorporate color centers based on nickel and tungsten, in situ into diamond using microwave-plasma-enhanced chemical vapor deposition. The fabrication of silicon–vacancy centers in nanodiamonds by microwave-plasma-enhanced chemical vapor deposition is discussed in addition.

diamond's exceptional properties for quantum information processing [2], a topic on which there have been many recent papers, and where a diamond colour centre single photon source is already commercially available. Biomedical applications of diamond are recognised, partly tribological and partly electrochemical, but lie outside the present group of papers. Processing and controlling diamond surfaces and interfaces with other materials in their environment are critical steps en route to exploitation. Boron-dopeddiamond has already found application in electro-analysis and in the bulk oxidation of dissolved species in solution [3]. Energy-related applications—ranging from high-power electronics [3] to a potential first wall of fusion reactors [4]—are further exciting potential applications. Even small and ugly diamonds have value. Their mechanical properties [5] dominate, with significant niche applications such as thermal sinks. The major applications for diamond to date exploit only a fraction of diamond's special properties: visual for status diamonds, and mechanical for working diamonds. Diamond physics reaches well beyond the usual laboratory, to the geological diamond formation processes in the Earth's mantle. Characterization of natural gem diamonds [6, 7] is one part of the detective story that allows us to understand the conditions under which they formed. It was only half a century ago that the scientific and technological challenges of diamond synthesis were met systematically. Today, most of the recent research on diamond has concentrated on synthetics, whether created using high pressure, high temperature (HPHT) techniques or chemical vapour deposition (CVD). The HPHT synthesis of diamond has advanced dramatically [8, 9] to the extent that dislocation birefringence [10] can be largely eliminated. In silicon technology, the elimination of dislocations was a major step in microelectronics. Now, even diamond can be synthesised containing virtually no

This work is focused on the development of a dual-layered diamond-coated tungsten carbide tool for machining titanium Ti-6Al-4V alloy. A hot-filament chemical vapor deposition technique was used to synthesize diamond films on tungsten carbide tools. A boron-dopeddiamond interlayer was added to a microcrystalline diamond layer in an attempt to improve the interface adhesion strength. The dual-layered diamond-coated tool was employed in machining at cutting speeds in the range of 70 to 150 m min-1 with a lower feed and a lower depth of cut of 0.5 mm rev-1 and 0.5 mm, respectively, to operate in the transition from adhesion- to diffusion-tool-wear and thereby arrive at suitable conditions for enhancing tool life. The proposed tool was then compared, on the basis of performance under real-time cutting conditions, with commercially available microcrystalline diamond, nanocrystalline diamond, titanium nitride and uncoated tungsten carbide tools. The life and surface finish of the proposed dual-layered tool and uncoated tungsten carbide were also investigated in interrupted cutting such as milling. The results of this study show a significant improvement in tool life and finish of Ti-6Al-4V parts machined with the dual-layered diamond-coated tool when compared with its uncoated counterpart. These results pave the way for the use of a low-cost tool, with respect to, polycrystalline diamond for enhancing both tool life and machining productivity in critical sectors fabricating parts out of titanium Ti-6Al-4V alloy. The application of this coating technology can also be extended to the machining of non-ferrous alloys owing to its better adhesion strength.

This work is focused on the development of a dual-layered diamond-coated tungsten carbide tool for machining titanium Ti-6Al-4V alloy. A hot-filament chemical vapor deposition technique was used to synthesize diamond films on tungsten carbide tools. A boron-dopeddiamond interlayer was added to a microcrystalline diamond layer in an attempt to improve the interface adhesion strength. The dual-layered diamond-coated tool was employed in machining at cutting speeds in the range of 70 to 150 m min −1 with a lower feed and a lower depth of cut of 0.5 mm rev −1 and 0.5 mm, respectively, to operate in the transition from adhesion- to diffusion-tool-wear and thereby arrive at suitable conditions for enhancing tool life. The proposed tool was then compared, on the basis of performance under real-time cutting conditions, with commercially available microcrystalline diamond, nanocrystalline diamond, titanium nitride and uncoated tungsten carbide tools. The life and surface finish of the proposed dual-layered tool and uncoated tungsten carbide were also investigated in interrupted cutting such as milling. The results of this study show a significant improvement in tool life and finish of Ti-6Al-4V parts machined with the dual-layered diamond-coated tool when compared with its uncoated counterpart. These results pave the way for the use of a low-cost tool, with respect to, polycrystalline diamond for enhancing both tool life and machining productivity in critical sectors fabricating parts out of titanium Ti-6Al-4V alloy. The application of this coating technology can also be extended to the machining of non-ferrous alloys owing to its better adhesion strength. (paper)

The measurement of the specific contact resistance, rho(sub C), and microstructural analysis at the metal/diamond interface were carried out for diamond with various acceptor concentrations, N(sub A), in order to understand the carrier transport mechanism at the metal/diamond interface. The rho(sub C) measurements were carried out for polycrystalline boron-doped semiconducting diamonds which were prepared by the microwave plasma chemical vapor deposition. The acceptor concentrations, estimated by the boron concentrations measured by secondary ion mass spectroscopy, ranged from 3 x 10(exp 18) to 3 x 10(exp 20)/cu cm. Ti and Mo films, which form carbides with diamond, were deposited on the diamonds using the electron-beam evaporation technique. The rho(sub C) values were measured by the cricular transmission line method before and after annealing at temperatures in the range of 400-600 C. The dependence of the rho(sub C) values on the acceptor concentrations suggested that the dominant transport mechanism was the field-emission for the diamond with N(sub A) around 10(exp 20)/cu cm and the thermionic-field-emission for the diamond with N(sub A) from 3 x 10(exp 18)/cu cm to 4 x 10(exp 19)/cu cm. The rho(sub C) values of the Ti contacts were observed to decrease upon annealing, whereas those of the Mo contacts decreased gradually with increasing annealing temperature. However, the rho(sub C) values of both the Ti and Mo contacts reached at the same value of approximately 1 x 10(exp -6) Ohm sq cm after annealing at 600 C for the diamonds with N(sub A) higher than 10(exp 20)/cu cm. Note that the rho(sub C) values of the Mo contact were extremely stable at high temperatures: the rho(sub C) values did not deteriorate after annealing at 600 C for more than 3 h. The thermally stable molybdenum carbide (alpha-Mo2C) and amorphous layers were observed at the Mo/diamond interface after annealing at 600 C by cross-sectional transmission electron microscopy and x-ray diffraction.

Although titanium and its alloys are widely used as implant material for orthopedic and dental applications they show only limited corrosion stability and osseointegration in different cases. The aim of the presented research was to develop and characterize a novel surface modification system from a thin diamond base layer and a hydroxyapatite (HAp) top coating deposited on the alloy Ti6Al4V widely used for implants in contact with bone. This coating system is expected to improve both the long-term corrosion behavior and the biocompatibility and bioactivity of respective surfaces. The diamond base films were obtained by Microwave Plasma Assisted Chemical Vapor Deposition (MW-PACVD); the HAp coatings were formed in aqueous solutions by electrochemically assisted deposition (ECAD) at varying polarization parameters. Scanning electron microscopy (SEM), Raman microscopy, and electrical conductivity measurements were applied to characterize the generated surface states; the calcium phosphate coatings were additionally chemically analyzed for their composition. The biological properties of the coating system were assessed using hMSC cells analyzing for cell adhesion, proliferation, and osteogenic differentiation. Varying MW-PACVD process conditions resulted in composite coatings containing microcrystalline diamond (MCD/Ti-C), nanocrystalline diamond (NCD), and boron-doped nanocrystalline diamond (B-NCD) with the NCD coatings being dense and homogeneous and the B-NCD coatings showing increased electrical conductivity. The ECAD process resulted in calcium phosphate coatings from stoichiometric and non-stoichiometric HAp. The deposition of HAp on the B-NCD films run at lower cathodic potentials and resulted both in the highest coating mass and the most homogenous appearance. Initial cell biological investigations showed an improved cell adhesion in the order B-NCD > HAp/B-NCD > uncoated substrate. Cell proliferation was improved for both investigated coatings whereas ALP

Although titanium and its alloys are widely used as implant material for orthopedic and dental applications they show only limited corrosion stability and osseointegration in different cases. The aim of the presented research was to develop and characterize a novel surface modification system from a thin diamond base layer and a hydroxyapatite (HAp) top coating deposited on the alloy Ti6Al4V widely used for implants in contact with bone. This coating system is expected to improve both the long-term corrosion behavior and the biocompatibility and bioactivity of respective surfaces. The diamond base films were obtained by Microwave Plasma Assisted Chemical Vapor Deposition (MW-PACVD); the HAp coatings were formed in aqueous solutions by electrochemically assisted deposition (ECAD) at varying polarization parameters. Scanning electron microscopy (SEM), Raman microscopy, and electrical conductivity measurements were applied to characterize the generated surface states; the calcium phosphate coatings were additionally chemically analyzed for their composition. The biological properties of the coating system were assessed using hMSC cells analyzing for cell adhesion, proliferation, and osteogenic differentiation. Varying MW-PACVD process conditions resulted in composite coatings containing microcrystalline diamond (MCD/Ti-C), nanocrystalline diamond (NCD), and boron-doped nanocrystalline diamond (B-NCD) with the NCD coatings being dense and homogeneous and the B-NCD coatings showing increased electrical conductivity. The ECAD process resulted in calcium phosphate coatings from stoichiometric and non-stoichiometric HAp. The deposition of HAp on the B-NCD films run at lower cathodic potentials and resulted both in the highest coating mass and the most homogenous appearance. Initial cell biological investigations showed an improved cell adhesion in the order B-NCD > HAp/B-NCD > uncoated substrate. Cell proliferation was improved for both investigated coatings whereas ALP

To form a 3D diamond detector electrodes were produced in diamond by a femtosecond laser-induced phase transition of diamond to graphite. The process parameters were varied to study the influence on electrode resistivity and induced stress. A technique for a relative measurement of stress induced in 3D diamond detectors is described. The detector was characterised with a 15 keV photon micro-beam (Diamond Light Source, Oxford) and a 4 MeV proton micro-beam (Ruder Bošković Institute, Zagreb). T...

The face centered cubic allotrope of carbon, diamond, is a semiconducting material which possesses a valuable combination of extreme properties such as super-hardness, highest thermal conductivity, chemical hardness, radiation hardness, wide bandgap and others. Advances in chemical vapour deposition (CVD) technology have lead to diamond becoming available in previously unattainable forms for example over large areas and with controllable purity. This has generated much research interest towards developing the knowledge and processing technology that would be necessary to fully exploit these extreme properties. Electronic devices fabricated on oxidised borondoped polycrystalline CVD diamond (PCD) displayed very poor and inconsistent characteristic. As a result, many electronic applications of polycrystalline diamond films were confined to ultra-violet (UV) and other forms of device which relied on the high intrinsic resistivity on undoped diamond films. If commercially accessible PCD films are to advance in areas which involve sophisticated electronic applications or to compete with existing semiconductors, the need for a more reliable and fully ionised dopant is paramount. This thesis describes a unique dopant discovered within the growth surface of PCD films. This dopant is related to hydrogen which arises during the growth of diamond films. The aim of this study is to characterise and identify possible applications for this form of dopant. The mechanism for carrier generation remains unknown and based on the experimental results in this work, a model is proposed. The Hall measurements conducted on this conductive layer revealed a p-type nature with promising properties for electronic device application. A more detail study based on electrical and surface science methods were carried out to identify the stability and operating conditions for this dopant. The properties of metal-semiconductor contacts on these surfaces were investigated. The fundamental knowledge

Uric acid (UA) is one of the principal effluents of urine wastewaters, widely used in agriculture as fertilizer, which is potentially dangerous and biorefractory. Hence, the degradation of UA (2,6,8-trihydroxy purine) in aqueous solution of pH 3.0 has been studied by conductive-diamond electrochemical oxidation. Hydroxyl radicals formed from water oxidation at the surface of boron-dopeddiamond anodes were the main oxidizing agents. Effects of current density and supporting electrolyte on the degradation rate and process efficiency are assessed. Results show that the increase of current density from 20 to 60 mA cm(-2) leads to a decrease in the efficiency of the electrochemical process. In addition, the best degradation occurred in the presence of NaCl as conductive electrolyte. Interestingly, an almost total mineralization of 50 ppm UA was obtained when anodic oxidation was performed at low current densities (20 mA cm(-2)) and in the presence of NaCl. This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of UA. The identification of UA transformation products was performed by high-performance liquid chromatography (HPLC). HPLC analysis of treated solutions revealed that oxalic acid and urea were the two intermediates found. Oxalic acid was the most persistent product. Based on detected intermediates and bibliographic research, a mechanism of UA mineralization by anodic oxidation has been proposed. Ionic chromatography analysis confirmed the release of [Formula: see text] and [Formula: see text] ions during UA mineralization.

Membrane separation is applied widely in many fields, while concentration polarization and membrane fouling, limiting its promotion and application greatly, are the bottlenecks in membrane application. Among which, membrane fouling is irreversible, membrane must be periodically cleaned or even replaced to restore permeability. Membrane cleaning has become one of Key issues in membrane separation areas. Considering incomparable electrochemical advantages of boron-dopeddiamond (BDD) film electrode over conventional electrode, a new composite membrane Ti/BDD, made by depositing CVD (chemical vapor deposition) boron-dopeddiamond film on titanium(Ti) membrane to modify porous titanium surface, that can be cleaned electrochemically is proposed. Feasibility of its preparation and application is discussed in this paper. Results shows that based on the unique electrochemical properties of diamond, cleaning level of this composite Ti/BDD membrane is significantly increased, making membrane life and efficiency improved prominently.

The selective doped overgrowth of 3D mesa patterns and trenches has become an essential fabrication step of advanced monolithic diamond-based power devices. The methodology here proposed combines the overgrowth of plasma-etched cylindrical mesa structures with the sequential growth of doping superlattices. The latter involve thin heavily borondoped epilayers separating thicker undoped epilayers in a periodic fashion. Besides the classical shape analysis under the scanning electron microscope relying on the appearance of facets corresponding to the main crystallographic directions and their evolution toward slow growing facets, the doping superlattices were used as markers in oriented cross-sectional lamellas prepared by focused ion beam and observed by transmission electron microscopy. This stratigraphic approach is shown here to be applicable to overgrown structures where faceting was not detectable. Intermediate growth directions were detected at different times of the growth process and the periodicity of the superlattice allowed to calculate the growth rates and parameters, providing an original insight into the planarization mechanism. Different configurations of the growth front were obtained for different sample orientations, illustrating the anisotropy of the 3D growth. Dislocations were also observed along the lateral growth fronts with two types of Burger vector: b 01 1 ¯ = /1 2 [ 01 1 ¯ ] and b 112 = /1 6 [ 112 ] . Moreover, the clustering of these extended defects in specific regions of the overgrowth prompted a proposal of two different dislocation generation mechanisms.

In the context of this thesis, new results about optical defects and intrinsic properties of diamond, AlN and AlGaN alloys have been obtained. The main experimental techniques used were low temperature cathodoluminescence and photoluminescence spectroscopy. First, different aspects of intentional and background doping of diamond were discussed. Thus, the most commonly observed green luminescence emission from borondoped HPHT diamonds has been studied by means of temperature dependent CL in a wide temperature range from 10 K to 450 K. One further subject, addressing deep defect nitrogen related luminescence was a study of nitrogen addition in combustion flame grown CVD diamond layers. Two further topics concern intrinsic excitations in diamond, free excitons and electron-hole drops. Several important parameters like the critical density, the critical temperature, and the low-temperature density inside the drops were evaluated. The ground state density of the electron-hole condensate in diamond is about {approx} 42 times larger than that in Si, and the critical temperature takes very high values in the range of 165K.. 173K. Cathodoluminescence investigations on epitaxial wurtzite AlN layers grown on sapphire, SiC, and Si substrates, have shown that although the material is generally of good optical quality, deep level luminescence are still dominating the spectra. Relatively sharp near-band-edge transitions have been observed in all three samples that exhibit significantly reduced line widths for the AlN/sapphire and the AlN/SiC samples. Much broader emission lines in the near band-gap region have been observed for the first time from the AlN sample grown on Si (111) substrate. Temperature dependent CL measurements and numerical line decompositions reveal complicated substructures in the excitonic lines. The temperature dependence of the energy positions and broadening parameters of the transition have been studied and compared with the other materials. Epitaxial Al

The use of diamond for advanced applications has been the dream of mankind for centuries. Until recently this dream has been realized only in the use of diamond for gemstones and abrasive applications where tons of diamonds are used on an annual basis. Diamond is the material system of choice for many applications, but its use has historically been limited due to the small size, high cost, and inconsistent (and typically poor) quality of available diamond materials until recently. The recent development of high quality, single crystal diamond crystal growth via the Chemical Vapor Deposition (CVD) process has allowed physcists and increasingly scientists in the life science area to think beyond these limitations and envision how diamond may be used in advanced applications ranging from quantum computing, to power generation and molecular imaging, and eventually even diamond nano-bots. Because of diamond's unique properties as a bio-compatible material, better understanding of diamond's quantum effects and a convergence of mass production, semiconductor-like fabrication process, diamond now promises a unique and powerful key to the realization of the bio-electronic devices being envisioned for the new era of medical science. The combination of robust in-the-body diamond based sensors, coupled with smart bio-functionalized diamond devices may lead to diamond being the platform of choice for bio-electronics. This generation of diamond based bio-electronic devices would contribute substantially to ushering in a paradigm shift for medical science, leading to vastly improved patient diagnosis, decrease of drug development costs and risks, and improved effectiveness of drug delivery and gene therapy programs through better timed and more customized solutions.

Although titanium and its alloys are widely used as implant material for orthopedic and dental applications they show only limited corrosion stability and osseointegration in different cases. The aim of the presented research was to develop and characterize a novel surface modification system from a thin diamond base layer and a hydroxyapatite (HAp) top coating deposited on the alloy Ti6Al4V widely used for implants in contact with bone. This coating system is expected to improve both the long-term corrosion behavior and the biocompatibility and bioactivity of respective surfaces. The diamond base films were obtained by Microwave Plasma Assisted Chemical Vapor Deposition (MW-PACVD); the HAp coatings were formed in aqueous solutions by electrochemically assisted deposition (ECAD) at varying polarization parameters. Scanning electron microscopy (SEM), Raman microscopy, and electrical conductivity measurements were applied to characterize the generated surface states; the calcium phosphate coatings were additionally chemically analyzed for their composition. The biological properties of the coating system were assessed using hMSC cells analyzing for cell adhesion, proliferation, and osteogenic differentiation. Varying MW-PACVD process conditions resulted in composite coatings containing microcrystalline diamond (MCD/Ti-C), nanocrystalline diamond (NCD), and boron-doped nanocrystalline diamond (B-NCD) with the NCD coatings being dense and homogeneous and the B-NCD coatings showing increased electrical conductivity. The ECAD process resulted in calcium phosphate coatings from stoichiometric and non-stoichiometric HAp. The deposition of HAp on the B-NCD films run at lower cathodic potentials and resulted both in the highest coating mass and the most homogenous appearance. Initial cell biological investigations showed an improved cell adhesion in the order B-NCD>HAp/B-NCD>uncoated substrate. Cell proliferation was improved for both investigated coatings whereas ALP

Diamond is a good candidate to replace silicon as sensor material in the innermost layer of a tracking detector at HL-LHC, due to its high radiation tolerance. After particle fluences of $10^{16}\\,{\\rm protons/cm^2}$, diamond sensors are expected to achieve a higher signal to noise ratio than silicon. In order to use low grade polycrystalline diamonds as sensors, electrodes inside the diamond bulk, so called 3D electrodes, are produced. Typically, this kind of diamond material has a lower charge collection distance (CCD) than higher grade diamond, which results in a decreased signal amplitude. With 3D electrodes it is possible to achieve full charge collection even in samples with low CCDs by decoupling the spacing of the electrodes from the thickness of the diamond bulk. The electrodes are produced using a femtosecond laser, which changes the phase of the diamond material. The phase changed material is conductive and identified as nanocrystalline graphite using Raman spectroscopy. Due to a crater like struct...

Diamond is perhaps the most versatile, efficient and radiation tolerant material available for use in beam detectors with a correspondingly wide range of applications in beam instrumentation. Numerous practical applications have demonstrated and exploited the sensitivity of diamond to charged particles, photons and neutrons. In this paper, a brief description of a generic diamond detector is given and the interaction of the CVD diamond detector material with protons, electrons, photons and neutrons is presented. Latest results of the interaction of sCVD diamond with 14 MeV mono-energetic neutrons are shown.

Iron nanoparticles were employed to induce the synthesis of diamond on molybdenum, silicon, and quartz substrates. Diamond films were grown using conventional conditions for diamond synthesis by hot filament chemical vapor deposition, except that dispersed iron oxide nanoparticles replaced the seeding. This approach to diamond induction can be combined with dip pen nanolithography for the selective deposition of diamond and diamond patterning while avoiding surface damage associated to diamond-seeding methods.

Full Text Available Direct electrode/neuron interfacing is a key challenge to achieve high resolution of neuronal stimulation required for visual prostheses. Neuronal interfacing on biomaterials commonly requires the presence of glial cells and/or protein coating. Nanocrystalline diamond is a highly mechanically stable biomaterial with a remarkably large potential window for the electrical stimulation of tissues. Using adult retinal cell cultures from rats, we found that glial cells and retinal neurons grew equally well on glass and nanocrystalline diamond. The use of a protein coating increased cell survival, particularly for glial cells. However, bipolar neurons appeared to grow even in direct contact with bare diamond. We investigated whether the presence of glial cells contributed to this direct neuron/diamond interface, by using purified adult retinal ganglion cells to seed diamond and glass surfaces with and without protein coatings. Surprisingly, these fully differentiated spiking neurons survived better on nanocrystalline diamond without any protein coating. This greater survival was indicated by larger cell numbers and the presence of longer neurites. When a protein pattern was drawn on diamond, neurons did not grow preferentially on the coated area, by contrast to their behavior on a patterned glass. This study highlights the interesting biocompatibility properties of nanocrystalline diamond, allowing direct neuronal interfacing, whereas a protein coating was required for glial cell growth.

Direct electrode/neuron interfacing is a key challenge to achieve high resolution of neuronal stimulation required for visual prostheses. Neuronal interfacing on biomaterials commonly requires the presence of glial cells and/or protein coating. Nanocrystalline diamond is a highly mechanically stable biomaterial with a remarkably large potential window for the electrical stimulation of tissues. Using adult retinal cell cultures from rats, we found that glial cells and retinal neurons grew equally well on glass and nanocrystalline diamond. The use of a protein coating increased cell survival, particularly for glial cells. However, bipolar neurons appeared to grow even in direct contact with bare diamond. We investigated whether the presence of glial cells contributed to this direct neuron/diamond interface, by using purified adult retinal ganglion cells to seed diamond and glass surfaces with and without protein coatings. Surprisingly, these fully differentiated spiking neurons survived better on nanocrystalline diamond without any protein coating. This greater survival was indicated by larger cell numbers and the presence of longer neurites. When a protein pattern was drawn on diamond, neurons did not grow preferentially on the coated area, by contrast to their behavior on a patterned glass. This study highlights the interesting biocompatibility properties of nanocrystalline diamond, allowing direct neuronal interfacing, whereas a protein coating was required for glial cell growth.

This is the first comprehensive book on the engineering of diamond optical devices. It will give readers an up-to-date account of the properties of optical quality synthetic diamond (single crystal, nanodiamond and polycrystalline) and reviews the large and growing field of engineering of diamond-based optical devices, with applications in quantum computation, nano-imaging, high performance lasers, and biomedicine. It aims to provide scientists, engineers and physicists with a valuable resource and reference book for the design and performance of diamond-based optical devices.

Four parcels of diamonds which either had or had not been cleaned using the usual techniques, chiefly involving etch in molten potassium nitrate were supplied by De Beers Diamond Research Laboratories. Each parcel contained about 40 stones, amounting to about 10 carats. Half the diamonds in each parcel were cleaned by a standard procedure involving half an hours ultrasonic agitation in a 20% solution of the commercial detergent 'Contrad' which is effectively a surfactant and chelating agent. Visual comparisons by a number of observers who were not told the stones' histories, established that these diamonds generally had a more sparkling appearance after the cleaning procedure had been applied

International audience; In the upper mantle, diamonds can potentially grow from various forms of media (solid, gas, fluid) with a range of compositions (e.g. graphite, C–O–H fluids, silicate or carbonate melts). Inclusions trapped in diamonds are one of the few diagnostic tools that can constrain diamond growth conditions in the Earth's mantle. In this study, inclusion-bearing diamonds have been synthesized to understand the growth conditions of natural diamonds in the upper mantle. Diamonds ...

Full Text Available The mineralization of diclofenac and acetaminophen has been studied by single anodic oxidation with boron-dopeddiamond (AO-BDD using an undivided electrolysis cell, by single heterogeneous catalytic photolysis with titanium dioxide (HCP-TiO2 and by the combination of both advanced oxidation processes. The results show that mineralization can be obtained with either single technology. The type of functional groups of the pollutant does not influence the results of the single AO-BDD process, but it has a significant influence on the results obtained with HCP-TiO2. A clear synergistic effect appears when both processes are combined showing improvements in the oxidation rate of more than 50% for diclofenac and nearly 200% for acetaminophen at the highest current exerted. Results obtained are explained in terms of the production of oxidants on the surface of BDD (primarily peroxodisulfate and the later homogeneous catalytic light decomposition of these oxidants in the bulk. This mechanism is consistent with the larger improvement observed at higher current densities, for which the production of oxidants is promoted.

This section is a compilation of notes and published international articles about the development of methods of depositing diamond films. Vapor deposition articles are included from American, Russian, and Japanese publications. The international competition to develop new deposition methodologies is stressed. The current status of chemical vapor deposition of diamond is assessed.

This paper examines the risk-return characteristics of investment grade gems (white diamonds, colored diamonds and other types of gems including sapphires, rubies, and emeralds). The transactions are coming from gem auctions and span the period 1999-2012. Over our time frame, the annual nominal USD

Full Text Available The paper generalizes on the one hand theory of kinematic-geometrical simulation of grinding processes by means of tools with working part as binding matrix with abrasive grains located in it in random manner, for example diamond grains, and on the other hand practical performance of combined grinding process, based on introduction of additional energy as electric discharges and called by the organization-developer (Kharkov Polytechnic Institute «diamond-spark grinding» as applied to processing by means of diamond wheel. Implementation of diamond-spark grinding technologies on the basis of developed generalized theoretical approach allows to use the tool with prescribed tool-life, moreover to make the most efficient use of it up to full exhausting of tool-life, determined by diamond-bearing thickness. Development is directed forward computer-aided manufacturing.

Natural diamond has been valued for its appearance and mechanical properties for at least two thousand years. As a gem stone diamond is unsurpassed. However, scientific work, especially in the last 20 years, has demonstrated that diamond has numerous surprising properties and many unique ones. Some of the extreme properties have been known for many years, but the true scale of diamond's other highly desirable features is still only coming to light as control in the synthesis of diamond, and h...

The recent development of chemical vapor deposition techniques for diamond growth enables bearings to be designed which exploit diamond's low friction and extreme resistance to wear. However, currently produced diamond coatings differ from natural diamond surfaces in that they are polycrystalline and faceted, and often contain appreciable amounts of non-diamond material (i.e. graphitic or amorphous carbon). Roughness, in particular, influences the friction and wear properties; rough coatings severely abrade softer materials, and can even wear natural diamond sliders. Nevertheless, the best available coatings exhibit friction coefficients as low as those of natural diamond and are highly resistant to wear. This paper reviews the tribological properties of natural diamond, and compares them with those of chemical vapor deposited diamond coatings. Emphasis is placed on the roles played by roughness and material transfer in controlling frictional behavior. (orig.)

The aim of this proposal is to demonstrate the key elements needed to construct a logical qubit in diamond by exploiting the remarkable quantum properties of the nitrogen-vacancy (NV) optical centre...

A diamond nanoparticle can be functionalized with a substituted dienophile under ambient conditions, and in the absence of catalysts or additional reagents. The functionalization is thought to proceed through an addition reaction.

Boron heterofullerenes were generated through arc-evaporation of doped graphite rods in a helium atmosphere. According to mass spectrometric analysis only mono-substituted fullerenes like C{sub 59}B, C{sub 69}B and higher homologues together with a large fraction of higher undoped fullerenes were extracted and enriched when pyridine was used as the solvent. XPS analysis of the extracts indicated the presence of two boron species with significantly different binding energies. One peak was assigned to borid acid. The second one corresponds to boron in the fullerene cage, which is mainly C{sub 59}B, according to the mass spectrum. This boron is in a somewhat higher oxidation state than that of ordinary boron-carbon compounds. The reported synthesis and extraction procedure opens a viable route for production of macroscopic amounts of these compounds. (author) 2 figs., 1 tab., 7 refs.

The use of diamond in electronic applications is not a new idea, but limitations in size and control of properties restricted the use of diamond to a few specialised applications. The vapour-phase synthesis of diamond, however, has facilitated serious interest in the development of diamond-based electronic devices. The process allows diamond films to be laid down over large areas. Both intrinsic and doped diamond films have a unique combination of extreme properties for high speed, high power and high temperature applications. The eleven chapters in Diamond: Electronic Properties and Applications, written by the world's foremost experts on the subject, give a complete characterisation of the material, in both intrinsic and doped forms, explain how to grow it for electronic applications, how to use the grown material, and a description of both passive and active devices in which it has been used with success. Diamond: Electronic Properties and Applications is a compendium of the available literature on the sub...

With the commissioning of the LHC in 2010 and upgrades expected in 2015, ATLAS and CMS are planning to upgrade their innermost tracking layers with radiation hard technologies. Chemical Vapor Deposition diamond has been used extensively in beam conditions monitors as the innermost detectors in the highest radiation areas of BaBar, Belle, CDF and all LHC experiments. This material is now being considered as a sensor material for use very close to the interaction region where the most extreme radiation conditions exist Recently the RD42 collaboration constructed, irradiated and tested polycrystalline and single-crystal chemical vapor deposition diamond sensors to the highest fluences expected at the super-LHC. We present beam test results of chemical vapor deposition diamond up to fluences of 1.8 x 10(16) protons/cm(2) illustrating that both polycrystalline and single-crystal chemical vapor deposition diamonds follow a single damage curve. We also present beam test results of irradiated complete diamond pixel m...

The graphitization and the change to amorphous state of diamond surface layer by ion implantation and its characteristics are reported. In the diamond surface, into which more than 10 16 ions/cm 2 was implanted, the diamond crystals are broken, and the structure changes to other carbon structure such as amorphous state or graphite. Accompanying this change of structure, the electric conductivity of the implanted layer shows two discontinuous values due to high resistance and low resistance. This control of structure can be done by the temperature of the base during the ion implantation into diamond. Also it is referred to that by the base temperature during implantation, the mutual change of the structure between amorphous state and graphite can be controlled. The change of the electric resistance and the optical characteristics by the ion implantation into diamond surface, the structural analysis by Raman spectroscopy, and the control of the structure of the implanted layer by the base temperature during implantation are reported. (K.I.)

Diamond is a promising material whose excellent physical properties foster its use for radiation detection applications, in particular in those hostile operating environments where the silicon-based detectors behavior is limited due to the high radiation fluence. Within this framework, the application of Technology Computer Aided Design (TCAD) simulation tools is highly envisaged for the study, the optimization and the predictive analysis of sensing devices. Since the novelty of using diamond in electronics, this material is not included in the library of commercial, state-of-the-art TCAD software tools. In this work, we propose the development, the application and the validation of numerical models to simulate the electrical behavior of polycrystalline (pc)CVD diamond conceived for diamond sensors for particle detection. The model focuses on the characterization of a physically-based pcCVD diamond bandgap taking into account deep-level defects acting as recombination centers and/or trap states. While a definite picture of the polycrystalline diamond band-gap is still debated, the effect of the main parameters (e.g. trap densities, capture cross-sections, etc.) can be deeply investigated thanks to the simulated approach. The charge collection efficiency due to β -particle irradiation of diamond materials provided by different vendors and with different electrode configurations has been selected as figure of merit for the model validation. The good agreement between measurements and simulation findings, keeping the traps density as the only one fitting parameter, assesses the suitability of the TCAD modeling approach as a predictive tool for the design and the optimization of diamond-based radiation detectors.

The paper presents the results on neutron irradiation of the diamond in a nuclear reactor. It is shown that the neutron irradiation stimulates the diamond transition to the amorphous state. At a temperature below 750 o K the time required for the diamond-graphite transition decreases with decreasing irradiation temperature. On the contrary, in irradiation at higher temperatures the time of diamond conversion into the amorphous state increases with decreasing but always remains shorter than in the absence of irradiation. (author)

This paper reviews existing and new applications of single crystal diamond, both natural and synthetic, in optical science. The traditional application is as transmissive components, making use of the very wide spectral transmission range, high thermal conductivity, and chemical inertness of diamond. Diamond windows for corrosive environments are well known; diamond surgical endoscope components are under development; and the use of sharpened diamonds as combined surgical cutting instruments and light pipes for internal illumination of the edge is commercial reality. The superb ability of diamond to conduct heat, combined with its very low thermal expansion coefficient makes it suitable for the transmission of high power laser energy, though there is a problem currently being addressed of a high surface reflection coefficient. It is very probable that CVD diamond-like films will form good anti-reflection coatings for diamond. In new applications, the technology of making diamond lenses is being developed. The use of diamond as a detector of ionising radiation is well known, but recent work shows its possibilities in thermoluminescent as well as conduction and pulse counting modes. There are further possibilities of using diamond for the detection and measurement of optical radiation. Examples are low, medium, and high intensity far ultraviolet (literature and the mechanical and thermal design of diamond "heat sink" substrates for semiconductor laser diodes is advancing rapidly.

bombardment a mechanically induced graphitisation, as opposed to a thermally activated transformation, may occur locally on collision with the CVD diamond. Two types of diamond-graphite interfaces were observed: (111) planes of diamond parallel to the a-b planes of graphite and (111) planes of diamond, smoothly within the plane, connected to a-b planes of graphite. The thesis concludes with a summary of the results, conclusions and recommendations for further work. This thesis deals with the wear of diamond occurring during frictional sliding contact between diamonds. In the introduction, a literature survey on friction, wear and polishing behaviour of diamond, with some emphasis on the anisotropy, is presented and earlier work is discussed. A review of the existing theories is given, a new hypothesis is proposed and key-experiments for verification are identified. Electron microscopical techniques such as High Resolution Electron Microscopy (HREM) imaging and Electron Energy Loss Spectroscopy are described a...

This compilation of figures and diagrams addresses the basic physical processes involved in the chemical vapor deposition of diamond. Different methods of deposition are illustrated. For each method, observations are made of the prominent advantages and disadvantages of the technique. Chemical mechanisms of nucleation are introduced.

At the end of the next decade an upgrade of the Large Hadron Collider (LHC) to High Luminosity LHC (HL-LHC) is planned which requires the development of new radiation tolerant sensor technology. Diamond is an interesting material for use as a particle detector in high radiation environments. The large band gap ($5.47\\,\\text{eV}$) and the large displacement energy suggest that diamond is a radiation tolerant detector material. In this Thesis the capability of Chemical Vapor Deposition (CVD) diamond as such a sensor technology is investigated. The radiation damage constant for $800\\,\\text{MeV}$ protons is measured using single crystalline CVD (scCVD) and polycrystalline CVD (pCVD) diamonds irradiated to particle fluences up to $12 \\times 10^{15}\\,\\text{p/cm}^2$. In addition the signal response of a pCVD diamond detector after an irradiation to $12 \\times 10^{15}\\,\\text{p/cm}^2$ is investigated to determine if such a detector can be operated efficiently in the expected HL-LHC environment. By using electrodes em...

This section is broken into four parts: (1) introduction, (2) natural IIa diamond, (3) importance of structure and composition, and (4) control of structure and properties. Conclusions of this discussion are that properties of chemical vapor deposited diamond films can compare favorably with natural diamond, that properties are anisotropic and are a strong function of structure and crystal perfection, that crystal perfection and morphology are functions of growth conditions and can be controlled, and that the manipulation of texture and thereby surface morphology and internal crystal perfection is an important step in optimizing chemically deposited diamond films for applications.

The application of diamond as a plasma facing material for fusion reactors can be limited by unknown reactions between diamond and the chamber materials transported by the plasma. Transformation of diamond to other structures can cause problems such as contamination of the plasma with loose particles or retention of gases. We have seen that diamond thin films are eroded under hydrogen plasma etching, but if silicon is present the growth of various carbon structures on diamond films is observed. We have produced carbon with different morphologies on diamond films including fibres, sheets with flower-like shapes and tubes and proposed growth mechanisms based on the results of scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Sample surfaces contain silicon and are oxidised having COO and CO groups as seen by XP S analysis. Raman analyses revealed a spectrum typical for graphite combined with that from diamond that remains on the surface after hydrogen bombardment. The results of this sturdy show the experimental conditions in which carbon fibres, sheets and tubes are produced under high-power hydrogen etching of diamond films and open the possibility to other applications such as catalysts, sensors and the production of electrodes. (Author)

The application of diamond as a plasma facing material for fusion reactors can be limited by unknown reactions between diamond and the chamber materials transported by the plasma. Transformation of diamond to other structures can cause problems such as contamination of the plasma with loose particles or retention of gases. We have seen that diamond thin films are eroded under hydrogen plasma etching, but if silicon is present the growth of various carbon structures on diamond films is observed. We have produced carbon with different morphologies on diamond films including fibres, sheets with flower-like shapes and tubes and proposed growth mechanisms based on the results of scanning electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Sample surfaces contain silicon and are oxidised having COO and CO groups as seen by XP S analysis. Raman analyses revealed a spectrum typical for graphite combined with that from diamond that remains on the surface after hydrogen bombardment. The results of this sturdy show the experimental conditions in which carbon fibres, sheets and tubes are produced under high-power hydrogen etching of diamond films and open the possibility to other applications such as catalysts, sensors and the production of electrodes. (Author)

We present the design and experimental progress on the diamond secondary emitter as an electron source for high average power injectors. The design criteria for average currents up to 1 A and charge up to 20 nC are established. Secondary Electron Yield (SEY) exceeding 200 in transmission mode and 50 in emission mode have been measured. Preliminary results on the design and fabrication of the self contained capsule with primary electron source and secondary electron emitter will also be presented.

A new research initiative will be undertaken to investigate the critical cutting depth concepts for single point diamond turning of brittle, amorphous materials. Inorganic glasses and a brittle, thermoset polymer (organic glass) are the principal candidate materials. Interrupted cutting tests similar to those done in earlier research are Ge and Si crystals will be made to obtain critical depth values as a function of machining parameters. The results will provide systematic data with which to assess machining performance on glasses and amorphous materials

Full Text Available In this study the authors make use of laser heating of HTHP industrial diamond, as well as the optically measured temperature profile of the diamond surface, to study temperature induced changes to the diamond structure, both chemically...

Diamond is one of the most extreme cases from a channelling point of view, having the smallest thermal vibration amplitude and the lowest atomic number of commonly-encountered crystals. These are the two parameters most important for determining channelling behaviour. It is of consiberable interest therefore to see how well the theories explaining and predicting the channeling properties of other substance, succeed with diamond. Natural diamond, although the best available form for these experiments, is rather variable in its physical properties. Part of the project was devoted to considering and solving the problem of obtaining reproducible results representative of the ideal crystal. Channelling studies were performed on several good crystals, using the Rutherford backscattering method. Critical angles for proton channelling were measured for incident energies from 0.6 to 4.5 MeV, in the three most open axes and three most open planes of the diamond structure, and for α-particle channelling at 0.7 and 1.0 MeV (He + ) in the same axes and planes. For 1.0 MeV protons, the crystal temperature was varied from 20 degrees Celsius to 700 degrees Celsius. The results are presented as curves of backscattered yield versus angle in the region of each axis or plane, and summarised in the form of tables and graphs. Generally the critical angles, axial minimum yields, and temperature dependence are well predicted by the accepted theories. The most valuable overall conclusion is that the mean thermal vibration amplitude of the atoms in a crytical determines the critical approach distance to the channel walls at which an ion can remain channelled, even when this distance is much smaller than the Thomas-Fermi screening distance of the atomic potential, as is the case in diamond. A brief study was made of the radiation damage caused by α-particle bombardment, via its effect on the channelling phenomenon. It was possible to hold damage down to negligible levels during the

The properties of the boron-dopeddiamond are sensitive to the boron concentration. A semiconducting behaviour occurs at low boron concentration and transport properties are given by a hopping-mechanism. The conductivity increases for higher boron concentration. The Mott metal to insulator transition takes place at a critical boron concentration. In the metallic phase superconductivity is observed. The critical temperatures of the superconducting transition are below 3 K. In this work, the influence of boron to the electronic properties, like conductivity and magneto resistance, was studied in the vicinity of the metal to insulator transition point. The superconducting properties (critical temperature, upper critical field) were studied down to 50 mK and compared to the conventional theory of the electron-phonon coupled superconductors. The properties of polycrystalline RuIn{sub 3} are reported in few publications to be metallic. In this work single crystals of this material were grown and analysed. We observe a semiconducting behaviour with an intrinsic gap of 0.4-0.5 eV. The previously reported metallic behaviour could be interpreted in this work as influence of the elementary indium in the samples. The measurements of the specific heat at low temperatures and LDA band structure calculations confirm the semiconducting properties and the value of the semiconducting gap. (orig.)

In this study, the electro-oxidation capacities of several electrode materials such as carbon-felt, carbon-fiber, carbon-graphite, platinum, lead dioxide, DSA (Dimensionally Stable Anode), (Ti/RuO2-IrO2), and BDD (Boron-DopedDiamond) were tested for the destruction of the antibiotic amoxicillin (AMX) in aqueous medium. BDD anode was more efficient than DSA to oxidize and mineralize totally AMX in water. Moreover, for BDD electrode we obtained very high electrolysis efficiency for the initial...

High resolution transmission electron microscopy (HRTEM) was used to study the nucleation and growth mechanism of diamond by hot filament chemical vapor deposition (HFCVD) process. A novel technique has shown a direct evidence for the formation of the diamond-like carbon layer 8-14 nm thick in which small diamond micro-crystallites were embedded. These diamond micro-crystallites were formed as a result of transformation of diamond-like carbon into diamond. The diamond micro-crystallites present in the amorphous diamond-like carbon layer provided nucleation sites for diamond growth. Large diamond crystallites were observed to grow from these micro-crystallites. The mechanism of diamond growth will be presented based on experimental findings.

Full Text Available Diamond has the highest thermal conductivity among known materials, and as such finds uses as an industrial tool in areas where dissipation of excess heat is a requirement. In this investigation we set up a laser system to heat a diamond sample...

Full Text Available In the present work, herbicide 2,4,5-trichlorophenoxyacetic acid, more commonly known as 2,4,5-T herbicide, has been completely mineralized (i.e. transformed into CO2 and H2O in saturated aqueous solutions using a semi-industrial electrochemical cell that contains a borondopeddiamond anode and a zirconium cathode. We have performed cyclic voltammetry, chronoamperometry and bulk electrolysis to give the optimization characteristics of the degradation of such a compound and its by-products. Bulk electrolysis in the potential region of electrolyte decomposition leads to the complete destruction of 2,4,5-T and its degradation intermediates by means of the electrogeneration of the highly reactive hydroxyl radicals. The evolution of the chemical oxygen demand (COD and the instant current efficiency (ICE during the degradation process is perfectly predicted by a theoretical mathematical model. HPLC and GC-MS have also been performed to highlight the evolution of the mother product and its degradation intermediates. Kinetic analysis of the obtained results has shown a fast destruction of the mother herbicide asserting a diffusion-controlled process. 2,4,5-trichlorophenol and quinone-based organic compounds have been depicted as aromatic intermediates, all of them transformed into short chains carboxylic acids before complete mineralization happens.

We propose a novel lithography process in which ion induced phase transfomations of diamond form sacrificial layers allowing the fabrication of small structures including micro-electromechanical systems (MEMS). We have applied this novel lithography to the fabrication of diamond microcavities, cantilevers and optical waveguides. In this paper we present preliminary experiments directed at the fabrication of suspended diamond disks that have the potential for operation as optical resonators. Such structures would be very durable and resistant to chemical attack with potential applications as novel sensors for extreme environments or high temperature radiation detectors. (author). 3 refs., 3 figs

During the last decade several applications of low-pressure diamond were developed. Main products are diamond heat-spreaders using its high thermal conductivity, diamond windows with their high transparency over a wide range of wavelengths and wear resistant tool coatings because of diamonds superhardness. A short description of the most efficient diamond deposition methods (microwave, DC-glow discharge, plasma-jet and arc discharge) is given. The production and applications of diamond layers with high thermal conductivity will be described. Problems of reproducibility of diamond deposition, the influence of impurities, the heat conductivity in electronic packages, reliability and economical mass production will be discussed. (author)

Diamond has been foreseen to replace silicon for high power, high frequency electronic applications or for devices that operates in harsh environments. However, diamond electronic devices are still in the laboratory stage due to the lack of large substrates and the complexity of diamond doping. On another hand, surface acoustic wave filters based on diamond are commercially available. Diamond is especially suited for acoustic applications because of its exceptional mechanical properties. The ...

Natural diamond, because of its well-known properties of tissue-equivalence, has recorded a wide spreading use in radiotherapy planning with electron linear accelerators. Artificial diamond dosimeters, as obtained by Chemical Vapour Deposition (CVD) could be capable to offer the same performances and they can be prepared in different volumes and shapes. The dosimeter sensitivity per unit volume may be easily proved to be better than standard ionization microchamber. We have prepared in our laboratory CVD diamond microchamber (diamond tips) in emispherical shape with an external diameter of 200 μm, which can be used both as X-ray beam profilometers and as microdosimeters for small field applications like stereotaxy and also for in vivo applications. These dosimeters, which are obtained on a wire substrate that could be either metallic or SiC or even graphite, display good performances also as ion or synchrotron X-rays detectors

This report describes DIAMONDS, a research project at Syracuse University, that is dedicated to producing both a methodology and corresponding tools to assist in the development of heterogeneous distributed software...

It is possible to ion implant patterns in diamond crystals at fluences below that which would impart visible damage and then to reveal those patterns by electrostatic charging and dusting. The charge distribution - and therefore the dust attachment - is related to the difference in electrical conductivity between the implanted region and the rest of the crystal. The technique may have applicability for ''fingerprinting'' or personalizing diamond gemstones. (author)

The object of the invention is the provision of a material capable of withstanding a high-temperature, corrosive and erosive environment for use as a ceramic-metal composite electrode current collector in the channel of a magnetohydrodynamic generator. (U.K.)

The beauty, value and mystique of exceptional quality diamonds such as the 603 carat Lesotho Promise, recovered from the Letseng Mine in 2006, help to drive a multi-billion dollar diamond exploration, mining and marketing industry that operates in some 45 countries across the globe. Five countries, Botswana, Russia, Canada, South Africa and Angola account for 83% by value and 65% by weight of annual diamond production, which is mainly produced by four major companies, De Beers, Alrosa, Rio Tinto and BHP Billiton (BHPB), which together account for 78% by value and 72% by weight of annual diamond production for 2007. During the last twelve years 16 new diamond mines commenced production and 4 re-opened. In addition, 11 projects are in advanced evaluation and may begin operations within the next five years. Exploration for diamondiferous kimberlites was still energetic up to the last quarter of 2008 with most work carried out in Canada, Angola, Democratic Republic of the Congo (DRC) and Botswana. Many kimberlites were discovered but no new economic deposits were outlined as a result of this work, except for the discovery and possible development of the Bunder project by Rio Tinto in India. Exploration methods have benefitted greatly from improved techniques of high resolution geophysical aerial surveying, new research into the geochemistry of indicator minerals and further insights into the formation of diamonds and the relation to tectonic/structural events in the crust and mantle. Recent trends in diamond marketing indicate that prices for rough diamonds and polished goods were still rising up to the last quarter of 2008 and subsequently abruptly sank in line with the worldwide financial crisis. Most analysts predict that prices will rise again in the long term as the gap between supply and demand will widen because no new economic diamond discoveries have been made recently. The disparity between high rough and polished prices and low share prices of publicly

This paper presents a recent study on the morphology variation on the lateral faces of a HPHT diamond seed by MPCVD method. Raman spectroscopy and SEM were used to display the morphological and structural evolution of the grown diamond. It has been observed that different types of carbon allotropes were deposited at different heights of the substrate. At the bottom of the substrate, the feature of the lateral face was dominated by vertically aligned graphite nanoplatelets. An increment of sp3 and sp2 hybridized carbons was found to take over at the region of approximately 100 μm above from the bottom followed by the increasing-size diamond grains. The high quality single crystalline diamond was formed at the top of the lateral face. We proposed that the temperature gradient around the substrate is responsible for variable features on the substrate lateral face. By optimizing the growth temperature, we have obtained an enlarged area of the lateral face with high quality single crystalline diamond. This work will provide both sp2 on sp3 carbon materials for the development of electrochemical sensors and electrodes, and a foundation for the diamond lateral face growth with high quality and high purity.

Finely divided carbon particles, including charcoal, lampblack, and diamond particles, have been used for ornamental and official tattoos since ancient times. With the recent development in nanoscience and nanotechnology, carbon-based nanomaterials (e.g., fullerenes, nanotubes, nanodiamonds) attract a great deal of interest. Owing to their low chemical reactivity and unique physical properties, nanodiamonds could be useful in a variety of biological applications such as carriers for drugs, genes, or proteins; novel imaging techniques; coatings for implantable materials; and biosensors and biomedical nanorobots. Therefore, it is essential to ascertain the possible hazards of nanodiamonds to humans and other biological systems. We have, for the first time, assessed the cytotoxicity of nanodiamonds ranging in size from 2 to 10 nm. Assays of cell viability such as mitochondrial function (MTT) and luminescent ATP production showed that nanodiamonds were not toxic to a variety of cell types. Furthermore, nanodiamonds did not produce significant reactive oxygen species. Cells can grow on nanodiamond-coated substrates without morphological changes compared to controls. These results suggest that nanodiamonds could be ideal for many biological applications in a diverse range of cell types.

Polycrystalline diamond (PCD) is regarded as among the hardest material in the world. Electrical Discharge Machining (EDM) typically used to machine this material because of its non-contact process nature. This investigation was purposely done to compare the EDM performances of PCD when using normal electrode of copper (Cu) and newly proposed graphitization catalyst electrode of copper nickel (CuNi). Two level full factorial design of experiment with 4 center points technique was used to study the influence of main and interaction effects of the machining parameter namely; pulse-on, pulse-off, sparking current, and electrode materials (categorical factor). The paper shows interesting discovery in which the newly proposed electrode presented positive impact to the machining performance. With the same machining parameters of finishing, CuNi delivered more than 100% better in Ra and MRR than ordinary Cu electrode.

This section is a compilation of transparency templates which describe the goals of the Office of Transportation Materials (OTM) Tribology Program. The positions of personnel on the OTM are listed. The role and mission of the OTM is reviewed. The purpose of the Tribology Program is stated to be `to obtain industry input on program(s) in tribology/advanced lubricants areas of interest`. The objective addressed here is to identify opportunities for cost effective application of diamond and diamond-like carbon in transportation systems.

Diamond has been considered for use in several medical applications due to its unique mechanical, chemical, optical, and biological properties. In this paper, methods for preparing synthetic diamond surfaces and particles are described. In addition, recent developments involving the use of diamond in prostheses, sensing, imaging, and drug delivery applications are reviewed. These developments suggest that diamond-containing structures will provide significant improvements in the diagnosis and...

Diamond exhibits a combination of properties which makes it attractive for neutron detection in hostile conditions. In the particular case of detection in a nuclear reactor, it is resilient to radiation, exhibits a natural low sensitivity to gamma rays, and its small size (as compared with that of gas ionisation chambers) enables fluency monitoring with a high position resolution. We report here on the use of synthetic CVD diamond as a solid state micro-fission chamber with U-235 converting material for in-core thermal neutron monitoring. Two types of thin diamond detectors were developed for this application. The first type of detector is fabricated using thin diamond membrane obtained by etching low-cost commercially available single crystal CVD intrinsic diamond, so called 'optical grade' material. Starting from a few hundred of micrometre thick samples, the sample is sliced with a laser and then plasma etched down to a few tenths of micrometre. Here we report the result obtained with a 17 μm thick device. The detection surface of this detector is equal to 1 mm 2 . Detectors with surfaces up to 1 cm 2 can be fabricated with this technique. The second type of detector is fabricated by growing successively two thin films of diamond, by the microwave enhanced chemical vapour deposition technique, on HPHT single crystal diamond. A first, a film of borondoped (p+) single crystal diamond, a few microns thick, is deposited. Then a second film of intrinsic diamond with a thickness of a few tens of microns is deposited. This results in a P doped, Intrinsic, Metal structure (PIM) structure in which the intrinsic volume id the active part of the detector. Here we report the results obtained with a 20 μm thick intrinsic whose detection surface is equal to 0.5 mm 2 , with the possibility to enlarge the surface of the detector up to 1 cm 2 . These two types of detector were tested at the VR-1 research reactor at the Czech Technical University in Prague. The

Carbon electrodes are widely used in electrochemistry due to their low cost, wide potential window, and low and stable background noise. Carbon-fiber electrodes (CFE) are commonly used to electrochemically measure “quantal” catecholamine release via exocytosis from individual cells, but it is difficult to integrate CFEs into lab-on-a-chip devices. Here we report the development of nitrogen doped diamond-like carbon (DLC:N) microelectrodes on a chip to monitor quantal release of catecholamines...

Alongside the CMS Pixel Luminosity Telescope (PLT) – installed last month (see here) – lie diamond detectors. No ordinary gems, these lab-grown diamonds will be playing a vital role in Run 2: differentiating signals from collision products with those from the beam background. The BCM detector's green "c-shaped" printed circuit board is mounted on the PLT/BCM carbon-fibre carriage ready for installation. Earlier this year, the CMS BRIL project installed beam condition monitors (BCM) at the heart of the CMS detector. Designed to measure the online luminosity and beam background as close as possible to the LHC beam pipe, the BCMs use radiation-hard diamonds to differentiate between background and collision signals. The BCM also protects the CMS silicon trackers from damaging beam losses, by aborting the beam if the signal currents measured are above an acceptable threshold. These new BCMs are designed with Run 2 bunches in mind. &ldq...

Interest in radiation detectors has supplied some of the impetus for improving the electronic properties of CVD diamond. In the present discussion, we will restrict our attention to polycrystalhne CVD material. We will focus on the evolution of these materials over the past decade and the correlation of detector performance with other properties of the material

Semiconducting diamond films have the potential for use as a material in which to build active electronic devices capable of operating at high temperatures or in high radiation environments. Ultimately, it is preferable to use low-defect-density single crystal diamond for device fabrication. We have previously investigated polycrystalline diamond films with transmission electron microscopy (TEM) and scanning electron microscopy (SEM), and homoepitaxial films with SEM-based techniques. This contribution describes some of our most recent observations of the microstructure of natural diamond single crystals and homoepitaxial diamond thin films using TEM.

Synthetic diamond is diamond produced by using chemical or physical processes. Like naturally occurring diamond it is composed of a three-dimensional carbon crystal. Due to its extreme physical properties, synthetic diamond is used in many industrial applications, such as drill bits and scratch-proof coatings, and has the potential to be used in many new application areas A brand new title from the respected Wiley Materials for Electronic and Optoelectronic Applications series, this title is the most up-to-date resource for diamond specialists. Beginning with an introduction to the pr

We discuss the use of diamond sensors in high-energy, high-i ntensity collider experiments. Re- sults from diamond sensor based beam conditions monitors in the ATLAS and CMS experiments at the CERN Large Hadron Collider (LHC) are presented and pla ns for diamond based luminosity monitors for the upcoming LHC run are described. We describe recent measurements on single crystal diamond sensors that indicate a polarization effec t that causes a reduction of charge col- lection efficiency as a function of particle flux. We conclude by describing new developments on the promising technology of 3D diamond sensors.

Polycrystalline diamond aggregates (framesites) contain silicates of eclogitic and peridotitic affinity (e.g. Kurat and Dobosi, 2000). The minerals occur mostly in interstices and are intimately intergrown with the diamonds, indicating contemporaneous crystallization within the diamond stability field in the Earth's mantle. In addition to silicates, rarer phases such as Fe-carbide can sometimes be found in framesites that record unusually low local oxygen fugacity at the time of their formation (Jacob et al., 2004). Furthermore, while most gem-sized diamonds have old, often Archaean formation ages, some polycrystalline diamond aggregates have been shown to form directly preceding the kimberlite eruption (Jacob et al., 2000). Thus, these samples may provide a unique source of information on the nature and timing of small scale processes that lead to diamond formation and complement evidence from gem-sized diamonds. Here, we present a study of micro- and nano-inclusions in diamonds from a polycrystalline diamond aggregate (framesite) from the Orapa Mine (Botswana) and combine results from TEM/FIB analyses with high-resolution computerized micro-tomography (HR-µCT) and electron microprobe analyses to further constrain the formation of diamond in the Earth's mantle. Results In total, 14 microinclusions from fifteen FIB foils were investigated. Micro- and nano-inclusions identified by TEM were smaller than 1µm down to ca. 50nm in size, and are both monomineralic and multi-phase. The cavities are often lath-shaped and oriented parallel to each other; many show lattice dislocations in the surrounding diamond. In addition, inclusions are found along open cracks within the diamond single crystals. Mineral phases in the microinclusions comprise rutile, omphacite and a FeS phase (pyrrhotite). The multiphase inclusions most often consist of cavities that are only partly occupied (less than 50% of the total space), suggesting that the empty space was originally filled by a

This paper describes the attributes that make diamond a unique material for infrared synchrotron beam experiments. New developments in diamond synthesised by Chemical Vapour Deposition (CVD) promise to extend the range of applications which have been hitherto limited by the availability and cost of large-size single-crystal diamond. Polycrystalline CVD diamond components such as large (100 mm) diameter windows with extremely good transparency over a wide spectral range are now commercially available. Properties of CVD diamond of relevance to optical applications, such as mechanical strength, thermal conductivity and absolute bulk absorption, are discussed. It is shown that although some of the properties of CVD diamond (similar to other polycrystalline industrial ceramics) are affected by the grain structure, currently produced CVD diamond optical components have the quality and performance required for numerous demanding applications

Full Text Available This special issue is intended to serve as a multidisciplinary forum covering broad aspects of the science, technology, and application of synthetic and natural diamonds. This special issue contains 12 papers, which highlight recent investigations and developments in diamond research related to the diverse problems of natural diamond genesis, diamond synthesis and growth using CVD and HPHT techniques, and the use of diamond in both traditional applications, such as mechanical machining of materials, and the new recently emerged areas, such as quantum technologies. The results presented in the contributions collected in this special issue clearly demonstrate that diamond occupies a very special place in modern science and technology. After decades of research, this structurally very simple material still poses many intriguing scientific questions and technological challenges. It seems undoubted that diamond will remain the center of attraction for many researchers for many years to come.

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With the commissioning of the LHC expected in 2009, and the LHC upgrades expected in 2012, ATLAS and CMS are planning for detector upgrades for their innermost layers requiring radiation hard technologies. Chemical Vapor Deposition (CVD) diamond has been used extensively in beam conditions monitors as the innermost detectors in the highest radiation areas of BaBar, Belle and CDF and is now planned for all LHC experiments. This material is now being considered as an alternate sensor for use very close to the interaction region of the super LHC where the most extreme radiation conditions will exist. Recently the RD42 collaboration constructed, irradiated and tested polycrystalline and single-crystal chemical vapor deposition diamond sensors to the highest fluences available. We present beam test results of chemical vapor deposition diamond up to fluences of 1.8 x 10^16 protons/cm^2 showing that both polycrystalline and single-crystal chemical vapor deposition diamonds follow a single damage curve allowing one t...

The objectives of this educational exercise were to demonstrate the high rate of heat flow from a synthetic diamond coupon and to compare it to a commonly used thermal conductor, such as copper. The principles of heat transfer by conduction and convection may also be demonstrated. A list of equipment and supplies and the procedure for the experiment are presented.

The present invention is directed to a nanotube coated with diamond or diamond-like carbon, a field emitter cathode comprising same, and a field emitter comprising the cathode. It is also directed to a method of preventing the evaporation of carbon from a field emitter comprising a cathode comprised of nanotubes by coating the nanotube with diamond or diamond-like carbon. In another aspect, the present invention is directed to a method of preventing the evaporation of carbon from an electron field emitter comprising a cathode comprised of nanotubes, which method comprises coating the nanotubes with diamond or diamond-like carbon.

Results from prototypes of a detector using chemical vapor deposited (CVD) diamond with embedded resistive electrodes in the bulk forming a 3D diamond device are presented. A detector system consisting of 3D devices based on poly-crystalline CVD (pCVD) diamond was connected to a multi-channel readout and successfully tested in a 120 GeV/c proton beam at CERN proving for the first time the feasibility of the 3D detector concept in pCVD for particle tracking applications. We also present beam test results on the dependence of signal size on incident particle rate in charged particle detectors based on poly-crystalline CVD diamond. The detectors were tested in a 260 MeV/c pion beam over a range of particle fluxes from 2 kHz/cm2 to 10 MHz/cm2 . The pulse height of the sensors was measured with pad readout electronics at a peaking time of 7 ns. Our data from the 2015 beam tests at PSI indicate that the pulse height of poly-crystalline CVD diamond sensor irradiated to 5×1014 neq/cm2 is independent of particle flux...

In metal forming, lubricants have to be used to prevent corrosion or to reduce friction and tool wear. From an economical and ecological point of view, the aim is to avoid the usage of lubricants. For dry deep drawing of aluminum sheets it is intended to apply locally micro-structured wear-resistant carbon based coatings onto steel tools. One type of these coatings are diamond layers prepared by chemical vapor deposition (CVD). Due to the high strength of diamond, milling processes are unsuitable for micro-structuring of these layers. In contrast to this, micro electrical discharge machining (micro EDM) is a suitable process for micro-structuring CVD-diamond layers. Due to its non-contact nature and its process principle of ablating material by melting and evaporating, it is independent of the hardness, brittleness or toughness of the workpiece material. In this study the deposition and micro electrical discharge machining of silicon incorporated CVD-diamond (Si-CVD-diamond) layers were presented. For this, 10 µm thick layers were deposited on molybdenum plates by a laser-induced plasma CVD process (LaPlas-CVD). For the characterization of the coatings RAMAN- and EDX-analyses were conducted. Experiments in EDM were carried out with a tungsten carbide tool electrode with a diameter of 90 µm to investigate the micro-structuring of Si-CVD-diamond. The impact of voltage, discharge energy and tool polarity on process speed and resulting erosion geometry were analyzed. The results show that micro EDM is a suitable technology for micro-structuring of silicon incorporated CVD-diamond layers.

A method of forming electrical contacts on a diamond substrate comprises producing a plasma ball using a microwave plasma source in the presence of a mixture of gases. The mixture of gases include a source of a p-type or an n-type dopant. The plasma ball is disposed at a first distance from the diamond substrate. The diamond substrate is maintained at a first temperature. The plasma ball is maintained at the first distance from the diamond substrate for a first time, and a UNCD film, which is doped with at least one of a p-type dopant and an n-type dopant, is disposed on the diamond substrate. The doped UNCD film is patterned to define UNCD electrical contacts on the diamond substrate.

The standard controller for a Pnuemo ASG 2500 Diamond Turning Machine, an Allen Bradley 8200, has been replaced with a custom high-performance design. This controller consists of four major components. Axis position feedback information is provided by a Zygo Axiom 2/20 laser interferometer with 0.1 micro-inch resolution. Hardware interface logic couples the computers digital and analog I/O channels to the diamond turning machine`s analog motor controllers, the laser interferometer, and other machine status and control information. It also provides front panel switches for operator override of the computer controller and implement the emergency stop sequence. The remaining two components, the control computer hardware and software, are discussed in detail below.

Single point diamond turning studies were made using a series of thermoplastic polymers with different glass transition temperatures. Variations in surface morphology and surface roughness were observed as a function of cutting speed. Lower glass transition temperatures facilitate smoother surface cuts and better surface finish. This can be attributed to the frictional heating that occurs during machining. Because of the very low glass transition temperatures in polymeric compared to inorganic glasses, the precision machining response can be very speed sensitive.

Selective deposition and abrasion, as well as etching in atomic oxygen or reduced-pressure air, have been used to prepare patterned polycrystalline diamond films which, on further processing by anisotropic Si etching, yield the microstructures of such devices as flow sensors and accelerometers. Both types of sensor have been experimentally tested in the respective functions of hot-wire anemometer and both single- and double-hinged accelerometer.

The unique combination of properties that diamond possesses are being exploited in both electronic and mechanical applications. An important step forward in the field has been the ability to grow thin film diamond by chemical vapour deposition (CVD) methods and to control parameters such as crystal orientation, dopant level and surface roughness. An extensive understanding of the surface of any potential electronic material is vital to fully comprehend its behaviour within device structures. The surface itself ultimately controls key aspects of device performance when interfaced with other materials. This study has provided insight into important chemical reactions on polycrystalline CVD diamond surfaces, addressing how certain surface modifications will ultimately affect the properties of the material. A review of the structure, bonding, properties and potential of diamond along with an account of the current state of diamond technology and CVD diamond growth is provided. The experimental chapter reviews bulk material and surface analytical techniques employed in this work and is followed by an investigation of cleaning treatments for polycrystalline CVD diamond aimed at removing non-diamond carbon from the surface. Selective acid etch treatments are compared and contrasted for efficacy with excimer laser irradiation and hydrogen plasma etching. The adsorption/desorption kinetics of potential dopant-containing precursors on polycrystalline CVD diamond surfaces have been investigated to compare their effectiveness at introducing dopants into the diamond during the growth stage. Both boron and sulphur-containing precursor compounds have been investigated. Treating polycrystalline CVD diamond in various atmospheres / combination of atmospheres has been performed to enhance electron field emission from the films. Films which do not emit electrons under low field conditions can be modified such that they emit at fields as low as 10 V/μm. The origin of this enhancement

This paper provides an up-to-date critical review of methods for diamond synthesis by lasers. A provisional classification of synthesizing methods is carried out, in order to present a varied and heterogeneous experimental work that is as clear as possible. Laser diamond CVD methods involve chemical processes in a carbon-containing system induced by specific absorption of laser radiation, while diamond PVD methods involve physical processes induced by an intense, highly-directed laser beam. D...

Single crystal diamond has been implanted at 1 MeV with 2 x 10 20 Ar/m 2 . Rutherford backscattering spectrometry in a channeled geometry revealed a broad amorphized region underlying a thin, partially crystalline layer. Raman spectroscopy disclosed modifications in the bonding characteristic of the appearance of non-diamond carbon. The complementary nature of the two analysis techniques is demonstrated. The Knoop hardness of the implanted diamond was reduced by implantation

The article presents information on diamond, which is regarded as the world's most popular gemstone. It states that there is strength in the covalent bonding between its carbon atoms, resulting to the strength of its physical properties. The presence of colors in diamonds may be attributed to the impurities that settle in the crystal lattice. Diamonds have been used as decorative items since the ancient era.

The objective was to study diamond film growth and its properties in order to enhance the laser damage threshold of substrate materials. Calculations were performed to evaluate laser induced thermal stress parameter, R(sub T) of diamond. It is found that diamond has several orders of magnitude higher in value for R(sub T) compared to other materials. Thus, the laser induced damage threshold (LIDT) of diamond is much higher. Diamond films were grown using a microwave plasma enhanced chemical vapor deposition (MPECVD) system at various conditions of gas composition, pressure, temperature, and substrate materials. A 0.5 percent CH4 in H2 at 20 torr were ideal conditions for growing of high quality diamond films on substrates maintained at 900 C. The diamond films were polycrystalline which were characterized by scanning electron microscopy (SEM) and Raman scattering spectroscopy. The top surface of the growing film is always rough due to the facets of polycrystalline film while the back surface of the film replicates the substrate surface. An analytical model based on two dimensional periodic heat flow was developed to calculate the effective in-plane (face parallel) diffusivity of a two layer system. The effective diffusivity of diamond/silicon samples was measured using a laser pulse technique. The thermal conductivity of the films was measured to be 13.5 W/cm K, which is better than that of a type Ia natural diamond. Laser induced damage experiments were performed on bare Si substrates, diamond film coated Si, and diamond film windows. Significant improvements in the LIDT were obtained for diamond film coated Si compared to the bare Si.

Diamond possesses excellent physical and electronic properties, and thus various applications that use diamond are under development. Additionally, the control of diamond geometry by etching technique is essential for such applications. However, conventional wet processes used for etching other materials are ineffective for diamond. Moreover, plasma processes currently employed for diamond etching are not selective, and plasma-induced damage to diamond deteriorates the device-performances. Here, we report a non-plasma etching process for single crystal diamond using thermochemical reaction between Ni and diamond in high-temperature water vapour. Diamond under Ni films was selectively etched, with no etching at other locations. A diamond-etching rate of approximately 8.7 μm/min (1000 °C) was successfully achieved. To the best of our knowledge, this rate is considerably greater than those reported so far for other diamond-etching processes, including plasma processes. The anisotropy observed for this diamond etching was considerably similar to that observed for Si etching using KOH.

A direct comparison between two complete intensity datasets, collected on the same sample loaded in two identical diamond-anvil pressure cells equipped, respectively, with beryllium and diamond backing plates was performed. The results clearly demonstrate that the use of diamond-backing plates...

Diamonds exist in all sizes, from the Hope Diamond to minuscule crystals only a few atoms across. The smallest of these diamonds are created naturally by the same processes that make petroleum. Recently, researchers discovered that these 'diamondoids' are formed in many different structural shapes, and that these shapes can be used like LEGO blocks for nanotechnology. This talk will discuss the discovery of these nano-size diamonds and highlight current SLAC/Stanford research into their applications in electronics and medicine.

In this study the applicability of chemical vapor deposition (CVD) diamond as a material for heat spreaders was investigated. Economical evaluations on the production of heat spreaders were also performed. For the diamond synthesis the hot-filament and microwave method were used respectively. The deposition parameters were varied in a way that free standing diamond layers with a thickness of 80 to 750 microns and different qualities were obtained. The influence of the deposition parameters on the relevant film properties was investigated and discussed. With both the hot-filament and microwave method it was possible to deposit diamond layers having a thermal conductivity exceeding 1200 W/mK and therefore to reach the quality level for commercial uses. The electrical resistivity was greater than 10 12 Ωcm. The investigation of the optical properties was done by Raman-, IR- and cathodoluminescence spectroscopy. Because of future applications of diamond-aluminium nitride composites as highly efficient heat spreaders diamond deposition an AIN was investigated. An improved substrate pretreatment prior to diamond deposition showed promising results for better performance of such composite heat spreaders. Both free standing layers and diamond-AIN composites could be cut by a CO2 Laser in Order to get an exact size geometry. A reduction of the diamond surface roughness was achieved by etching with manganese powder or cerium. (author)

Full Text Available This paper provides an up-to-date critical review of methods for diamond synthesis by lasers. A provisional classification of synthesizing methods is carried out, in order to present a varied and heterogeneous experimental work that is as clear as possible. Laser diamond CVD methods involve chemical processes in a carbon-containing system induced by specific absorption of laser radiation, while diamond PVD methods involve physical processes induced by an intense, highly-directed laser beam. Different methods involving coupled, simultaneous action of lasers and classic CVD agents are suggested and discussed as prospective approaches for diamond synthesis.

A substantially all diamond transistor with an electrically insulating substrate, an electrically conductive diamond layer on the substrate, and a source and a drain contact on the electrically conductive diamond layer. An electrically insulating diamond layer is in contact with the electrically conductive diamond layer, and a gate contact is on the electrically insulating diamond layer. The diamond layers may be homoepitaxial, polycrystalline, nanocrystalline or ultrananocrystalline in various combinations.A method of making a substantially all diamond self-aligned gate transistor is disclosed in which seeding and patterning can be avoided or minimized, if desired.

Diamond is an exciting material with many outstanding properties; see, for example Field J E (ed) 1979 The Properties of Diamond (London: Academic) and Field J E (ed) 1992 The Properties of Natural and Synthetic Diamond (London: Academic). It is pre-eminent as a gemstone, an industrial tool and as a material for solid state research. Since natural diamonds grew deep below the Earth's surface before their ejection to mineable levels, they also contain valuable information for geologists. The key to many of diamond's properties is the rigidity of its structure which explains, for example, its exceptional hardness and its high thermal conductivity. Since 1953, it has been possible to grow synthetic diamond. Before then, it was effectively only possible to have natural diamond, with a small number of these found in the vicinity of meteorite impacts. Techniques are now available to grow gem quality synthetic diamonds greater than 1 carat (0.2 g) using high temperatures and pressures (HTHP) similar to those found in nature. However, the costs are high, and the largest commercially available industrial diamonds are about 0.01 carat in weight or about 1 mm in linear dimension. The bulk of synthetic diamonds used industrially are 600 µm or less. Over 75% of diamond used for industrial purposes today is synthetic material. In recent years, there have been two significant developments. The first is the production of composites based on diamond; these materials have a significantly greater toughness than diamond while still maintaining very high hardness and reasonable thermal conductivity. The second is the production at low pressures by metastable growth using chemical vapour deposition techniques. Deposition onto non-diamond substrates was first demonstrated by Spitsyn et al 1981 J. Cryst. Growth 52 219-26 and confirmed by Matsumoto et al 1982 Japan J. Appl. Phys. 21 L183-5. These developments have added further to the versatility of diamond. Two other groups of

Natural diamonds are fabulous probes of the deep Earth Interior. They are the evidence of the deep storage of volatile elements, carbon at first, but also hydrogen and chlorine trapped as hydrous fluids in inclusions. The study of diamond growth processes in the lithosphere and mantle helps for our understanding of volatile elements cycling between deep reservoirs. We know now that inclusion-bearing diamonds similar to diamonds found in nature (i.e. polycrystalline, fibrous and coated diamonds) can grow in hydrous fluids or melts (Bureau et al., GCA 77, 202-214, 2012). Therefore, we propose that the best environment to promote such diamonds is the subduction factory, where highly hydrous fluids or melts are present. When oceanic plates are subducted in the lithosphere, they carry an oceanic crust soaked with seawater. While the slabs are traveling en route to the mantle, dehydration processes generate saline fluids highly concentrated in NaCl. In the present study we have experimentally shown that diamonds can grow from the saline fluids (up to 30 g/l NaCl in water) generated in subducted slabs. We have performed multi-anvil press experiments at 6-7 GPa and from 1300 to 1400°C during 6:00 hours to 30:00 hours. We observed large areas of new diamond grown in epitaxy on pure diamond seeds in salty hydrous carbonated melts, forming coated gems. The new rims are containing multi-component primary inclusions. Detailed characterizations of the diamonds and their inclusions have been performed and will be presented. These experimental results suggest that multi-component salty fluids of supercritical nature migrate with the slabs, down to the deep mantle. Such fluids may insure the first stage of the deep Earth's volatiles cycling (C, H, halogen elements) en route to the transition zone and the lower mantle. We suggest that the subduction factory may also be a diamond factory.

Full Text Available Diamond film growth was studied using chemical vapor deposition (CVD. A special equipment was build in-house, employing a welding torch, and substrate holder with a water-cooling system. Acetylene and oxygen were used as combustion gases and the substrate was tungsten carbide cobalt. It was found that surface treatments, such as diamond powder scratching or acid etching, increase the adhesion and prevent the film peel-off. Diamond powder scratching and combined diamond powder scratching with acid etching gave the similar diamond film structure with small grain and slightly rough surface. The diamond film obtained with both treatments has high adhesion and can withstand internal stress better than ones obtained by untreated surface or acid etching alone. It was also found that higher substrate temperature produced smoother surface and more uniform diamond grain.

Jul 22, 2011 ... In March 2002, an international meeting in Ottawa, Canada concluded a remarkable agreement to end "conflict" or "blood" diamonds. Conflict diamonds have been used by rebels in Sierra Leone, the Democratic Republic of the Congo, and Angola to buy weapons and to fuel horrific wars that have so far, ...

The brief review of the literature is devoted to synthesis of nanocrystalline diamond films. It is shown that the CVD method is an effective way for deposition of such nanostructures. The basic technological methods that allow limit the size of growing diamond crystallites in the film are studied.

We present a new method based on femtosecond laser ablation for the fabrication of statically bent diamond crystals. Using this method, curvature radii of 1 m can easily be achieved, and the curvature obtained is very uniform. Since diamond is extremely tolerant to high radiation doses, partly due...

Abstract: This paper examines the risk-return characteristics of investment grade gems (white diamonds, colored diamonds and other types of gems including sapphires, rubies, and emeralds). The transactions are coming from gem auctions and span the period 1999-2012. Over our time frame, the annual

Jul 15, 2011 ... Their report, The Heart of the Matter: Sierra Leone, Diamonds and Human Security, has attracted worldwide attention since it was published last year and has contributed to major changes in the international diamond industry. In 1999, the International Development Research Centre (IDRC) and several ...

A technique has been established to grow large diamonds up to 2 cm. The crystals are bulky polyhedron with yellow, blue, green or brown color as well as colorless, which depend on impurities. The impurities incorporated into the diamond are limited, i.e. nitrogen, boron, nickel, cobalt, silicon and phosphorus.

Full Text Available The most effective method for finish machining of hard-metals and alloys is to use the diamond grinding wheels for grinding. An application of diamond wheels significantly increases the employee output, reduces costs, and raises manufacturing efficiency with achieving the high performance properties of treated surfaces.During grinding a working surface of diamond wheel wears out. It adversely affects the cutting capability of the diamond grains, and depending on the grinding conditions can occur through different mechanisms. Wear of diamond wheel causes distortion of its shape and reduces cutting properties. However, dressing of diamond wheels is a complicated and time-consuming operation in terms of manufacturing technique.Methods to make dressing of diamond grinding wheel have different types of classification. Classification of dressing methods by the type of energy used is as follows: mechanical, chemical, electrophysical, electromechanical, and electrochemical. All these methods have their advantages and disadvantages.Electrochemical method of dressing is the most productive and efficient. Electrochemical method comprises anode-mechanical dressing and electrochemical (electrolytic one. The paper presents the electrochemical in-process dressing (ECD and the electrolytic in-process dressing (ELID.The source of energy, grinding a wheel with metal bond, and an electrode are necessary for providing ELID. The ELID consists of several stages. The first stage is preliminary electrolytic dressing of diamond wheel. The electrolyte is placed into the gap between the wheel and electrode. The bond of the wheel is oxidized. An insulating layer is formed. It reduces an electrical conductivity of the wheel and controls consumption of diamond grains, as well as polishes the surface of the work piece. Further, the insulating layer is destroyed. The cycle of dressing begins anew.The ECD proceeds in the same way as ELID. However during the ECD-process there

An electrode array which has applications for neural stimulation and sensing. The electrode array can include a large number of electrodes each of which is flexibly attached to a common substrate using a plurality of springs to allow the electrodes to move independently. The electrode array can be formed from a combination of bulk and surface micromachining, with electrode tips that can include an electroplated metal (e.g. platinum, iridium, gold or titanium) or a metal oxide (e.g. iridium oxide) for biocompatibility. The electrode array can be used to form a part of a neural prosthesis, and is particularly well adapted for use in an implantable retinal prosthesis where the electrodes can be tailored to provide a uniform gentle contact pressure with optional sensing of this contact pressure at one or more of the electrodes.

An electrode array is disclosed which has applications for neural stimulation and sensing. The electrode array, in certain embodiments, can include a plurality of electrodes each of which is flexibly attached to a common substrate using a plurality of springs to allow the electrodes to move independently. In other embodiments of the electrode array, the electrodes can be fixed to the substrate. The electrode array can be formed from a combination of bulk and surface micromachining, and can include electrode tips having an electroplated metal (e.g. platinum, iridium, gold or titanium) or a metal oxide (e.g. iridium oxide) for biocompatibility. The electrode array can be used to form a part of a neural prosthesis, and is particularly well adapted for use in an implantable retinal prosthesis.

The status of material development of poly-crystalline chemical vapor deposition (CVD) diamond is presented. We also present beam test results on the independence of signal size on incident par-ticle rate in charged particle detectors based on un-irradiated and irradiated poly-crystalline CVD diamond over a range of particle fluxes from 2 kHz/cm2 to 10 MHz/cm2. The pulse height of the sensors was measured with readout electronics with a peaking time of 6 ns. In addition the first beam test results from 3D detectors made with poly-crystalline CVD diamond are presented. Finally the first analysis of LHC data from the ATLAS Diamond Beam Monitor (DBM) which is based on pixelated poly-crystalline CVD diamond sensors bump-bonded to pixel readout elec-tronics is shown.

The quantum properties of the nitrogen vacancy (NV) centre in diamond has prompted rapid growth in diamond research. This initial growth was driven by the fact the NV centre provides an 'easy' to manipulate quantum system along with opening up the possibility of a new material to deliver a solid state quantum computer. The NV defect is now moving from a quantum curiosity to a commercial development platform for a range of application such as as gyroscopes, timing and magnetometry as well as the more traditional quantum technologies such as quantum encryption and quantum simulation. These technologies are pushing the development needs of the material, and the processing of that material. The paper will describes the advances in CVD diamond synthesis with special attention to getting NV defects close to the surface of the diamond and how to process the material for diamond quantum optical applications. (author)

Diamond is increasingly used in biomedical applications because of its unique properties such as the highest thermal conductivity, good optical properties, high electrical breakdown voltage as well as excellent biocompatibility and chemical resistance. Diamond has also been introduced as an excellent substrate to make the functional microchip structures for electrophoresis, which is the most popular separation technique for the determination of analytes. In this investigation, a diamond electrophoretic chip was manufactured by a replica method using a silicon mold. A polycrystalline 300 micron-thick diamond layer was grown by the microwave plasma-assisted CVD (MPCVD) technique onto a patterned silicon substrate followed by the removal of the substrate. The geometry of microstructure, chemical composition, thermal and optical properties of the resulting free-standing diamond electrophoretic microchip structure were examined by CLSM, SFE, UV-Vis, Raman, XRD and X-ray Photoelectron Spectroscopy, and by a modified laser flash method for thermal property measurements.

The charge collection properties of CVD diamond have been investigated with ionising radiation. In this study two CVD diamond samples, prepared with electrical contacts have been used as solid state ionisation chambers. The diamonds have been studied with beta particles and 10 keV photons, providing a homogeneous ionisation density and with protons and alpha particles which are absorbed in a thin surface layer. For the latter case a strong decrease of the signal as function of time is observed, which is attributed to polarisation effects inside the diamond. Spatially resolved measurements with protons show a large variation of the charge collection efficiency, whereas for photons and minimum ionising particles the response is much more uniform and in the order of 18%. These results indicate that the applicability of CVD diamond as a position sensitive particle detector depends on the ionisation type and appears to be promising for homogeneous ionisation densities as provided by relativistic charged particles.

With the planned upgrade of the LHC to High-Luminosity-LHC [1], the general purpose experiments ATLAS and CMS are planning to upgrade their innermost tracking layers with more radiation tolerant technologies. Chemical Vapor Deposition CVD diamond is one such technology. CVD diamond sensors are an established technology as beam condition monitors in the highest radiation areas of all LHC experiments. The RD42-collaboration at CERN is leading the effort to use CVD diamond as a material for tracking detectors operating in extreme radiation environments. An overview of the latest developments from RD42 is presented including the present status of diamond sensor production, a study of pulse height dependencies on incident particle flux and the development of 3D diamond sensors.